JP2019112488A - Stain resistance imparting agent, coating agent and article - Google Patents

Stain resistance imparting agent, coating agent and article Download PDF

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JP2019112488A
JP2019112488A JP2017245029A JP2017245029A JP2019112488A JP 2019112488 A JP2019112488 A JP 2019112488A JP 2017245029 A JP2017245029 A JP 2017245029A JP 2017245029 A JP2017245029 A JP 2017245029A JP 2019112488 A JP2019112488 A JP 2019112488A
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JP6922720B2 (en
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桐澤　理恵
Rie Kirisawa
理恵 桐澤
博 松沢
Hiroshi Matsuzawa
博 松沢
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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Abstract

【課題】耐汚染性付与剤、該耐汚染性付与剤を含有するコーティング剤、及び該コーティング剤の塗膜を有する物品の提供。【解決手段】芳香族炭化水素置換基を含む構造単位（Ｕ１）及び芳香族炭化水素置換基を含まない構造単位（Ｕ２）を有するポリシロキサン（ａ１）と、前記（ａ１）と反応し得る基を有する重合体が特定の結合により結合した複合樹脂（Ａ）が、媒体中に溶解又は分散した耐汚染性付与剤であり、前記複合樹脂（Ａ）中の前記ポリシロキサン（ａ１）が７５〜９９質量％、前記ポリシロキサン（ａ１）中の前記構造単位（Ｕ１）が１０〜５５質量％である耐汚染性付与剤。【選択図】なしPROBLEM TO BE SOLVED: To provide an article having a stain resistance imparting agent, a coating agent containing the stain resistance imparting agent, and a coating film of the coating agent. SOLUTION: A polysiloxane (a1) having a structural unit (U1) containing an aromatic hydrocarbon substituent and a structural unit (U2) not containing an aromatic hydrocarbon substituent and a group capable of reacting with the above (a1). The composite resin (A) in which the polymer having the above is bonded by a specific bond is a stain resistance imparting agent dissolved or dispersed in the medium, and the polysiloxane (a1) in the composite resin (A) is 75 to 75 to A stain resistance imparting agent having 99% by mass and the structural unit (U1) in the polysiloxane (a1) being 10 to 55% by mass. [Selection diagram] None

Description

本発明は、コーティング剤をはじめとする様々な用途に使用可能な耐汚染性付与剤に関するものである。   The present invention relates to a stain resistance imparting agent that can be used in various applications including coating agents.

塗料分野において、建築物、車両、大型構造物等の多くは、メンテナンスフリーで長期に渡る美観維持が要求されており、塗膜の耐候性や耐汚染性の向上が課題となっていた。   In the paint field, many buildings, vehicles, large-sized structures, etc. are required to be maintenance-free and maintain aesthetic appearance over a long period of time, and improvement in weather resistance and contamination resistance of a coating film has been a problem.

このような中、各種塗膜物性に優れる材料として、無機材料と有機材料とを複合化した硬化性樹脂組成物が提案されている（例えば、特許文献１参照。）。しかしながら、この硬化性樹脂組成物の塗膜は、耐候性等に優れるものの、耐汚染性の発現は十分でなかった。   Among these, as a material excellent in various coating film properties, a curable resin composition in which an inorganic material and an organic material are complexed has been proposed (see, for example, Patent Document 1). However, although the coating film of this curable resin composition is excellent in the weather resistance etc., expression of stain resistance was not enough.

そこで、耐汚染性に優れた塗膜を形成可能な材料が求められていた。   Then, the material which can form the coating film excellent in contamination resistance was called for.

特開平１１−２７９４０８号公報JP-A-11-279408

本発明が解決しようとする課題は、各種材料に耐汚染性を付与可能な耐汚染性付与剤、該耐汚染性付与剤を含有するコーティング剤、及び該コーティング剤の塗膜を有する物品を提供することである。   The problem to be solved by the present invention is to provide a stain resistance imparting agent capable of imparting stain resistance to various materials, a coating agent containing the stain resistance imparting agent, and an article having a coating film of the coating agent. It is to be.

本発明者等は、上記課題を解決すべく鋭意研究を重ねた結果、特定のポリシロキサン及び特定の重合体セグメントが結合した複合樹脂が媒体中に溶解又は分散した耐汚染性付与剤が、保存安定性に優れ、各種水性樹脂に添加することで、耐汚染性に優れた塗膜を形成可能であることを見出し、本発明を完成させた。   As a result of intensive studies to solve the above problems, the present inventors have found that a stain resistance-imparting agent in which a specific polysiloxane and a composite resin to which a specific polymer segment is bound is dissolved or dispersed in a medium is stored. It discovered that it was excellent in stability and it was possible to form the coating film excellent in stain resistance by adding to various aqueous resins, and completed the present invention.

すなわち、本発明は、一般式（１）又は（２）で表される構造単位（Ｕ１）、及び一般式（３）で表される構造単位（Ｕ２）を有するポリシロキサン（ａ１）と重合体（ａ２）とが一般式（４）で表される結合により結合した複合樹脂（Ａ）が、媒体中に溶解又は分散している硬化性樹脂組成物であって、前記複合樹脂（Ａ）中の前記ポリシロキサン（ａ１）が７５〜９９質量％であり、前記ポリシロキサン（ａ１）中の前記構造単位（Ｕ１）が１０〜５５質量％であることを特徴とする耐汚染性付与剤に関する。   That is, in the present invention, a polysiloxane (a1) having a structural unit (U1) represented by the general formula (1) or (2) and a structural unit (U2) represented by the general formula (3) and a polymer A curable resin composition in which a composite resin (A) in which (a2) and (a) are bonded by a bond represented by the general formula (4) is dissolved or dispersed in a medium, and in the composite resin (A) The present invention relates to a stain resistance imparting agent characterized in that the amount of the polysiloxane (a1) is 75 to 99% by mass, and the amount of the structural unit (U1) in the polysiloxane (a1) is 10 to 55% by mass.

Figure 2019112488
Figure 2019112488

Figure 2019112488
（一般式（１）、（２）中のＲ１は芳香族炭化水素置換基を表し、Ｒ２は芳香族炭化水素置換基又はアルキル基を表す。）
Figure 2019112488
 (R 1 in the general formulas (1) and (2) represents an aromatic hydrocarbon substituent, and R 2 represents an aromatic hydrocarbon substituent or an alkyl group.)

Figure 2019112488
（一般式（３）中のＲ３はメチル基又はエチル基を表す。）
Figure 2019112488
 (R 3 in general formula (3) represents a methyl group or an ethyl group.)

Figure 2019112488
Figure 2019112488

本発明の耐汚染性付与剤を含有する材料は、耐汚染性等に優れた塗膜を形成できることから、コーティング剤等に好適に使用することができる。   The material containing the stain resistance imparting agent of the present invention can be suitably used as a coating agent and the like because it can form a coating film excellent in stain resistance and the like.

本発明の耐汚染性付与剤は、一般式（１）又は（２）で表される構造単位（Ｕ１）、及び一般式（３）で表される構造単位（Ｕ２）を有するポリシロキサン（ａ１）と重合体（ａ２）とが一般式（４）で表される結合により結合した複合樹脂（Ａ）が、媒体中に溶解又は分散している硬化性樹脂組成物であって、前記複合樹脂（Ａ）中の前記ポリシロキサン（ａ１）が７５〜９９質量％であり、前記ポリシロキサン（ａ１）中の前記構造単位（Ｕ１）が１０〜５５質量％であるものである。   The stain resistance imparting agent of the present invention is a polysiloxane (a1) having a structural unit (U1) represented by the general formula (1) or (2) and a structural unit (U2) represented by the general formula (3) A curable resin composition in which the composite resin (A) in which the polymer (a2) and the polymer (a2) are bonded by a bond represented by the general formula (4) is dissolved or dispersed in a medium, The polysiloxane (a1) in (A) is 75 to 99% by mass, and the structural unit (U1) in the polysiloxane (a1) is 10 to 55% by mass.

まず、前記複合樹脂（Ａ）について説明する。前記複合樹脂（Ａ）は、前記ポリシロキサン（ａ１）と前記重合体（ａ２）とが前記一般式（４）で表される結合により結合したものである。   First, the composite resin (A) will be described. The composite resin (A) is obtained by bonding the polysiloxane (a1) and the polymer (a2) by a bond represented by the general formula (4).

前記複合樹脂（Ａ）の形態としては、例えば、前記ポリシロキサン（ａ１）が前記重合体（ａ２）の側鎖として化学的に結合したグラフト構造を有する複合樹脂や、前記重合体（ａ２）と前記ポリシロキサン（ａ１）とが化学的に結合したブロック構造を有する複合樹脂等が挙げられる。   As a form of the composite resin (A), for example, a composite resin having a graft structure in which the polysiloxane (a1) is chemically bonded as a side chain of the polymer (a2), or the polymer (a2) Composite resin etc. which have the block structure which the said polysiloxane (a1) couple | bonded chemically are mentioned.

前記一般式（４）で表される結合は、前記ポリシロキサン（ａ１）が有するシラノール基及び／または加水分解性シリル基と、前記重合体（ａ２）が有するシラノール基及び／または加水分解性シリル基とが脱水縮合反応することにより生じる。したがって、前記一般式（４）中、炭素原子は前記重合体（ａ２）の一部分を構成し、酸素原子のみに結合したケイ素原子は、前記ポリシロキサン（ａ１）の一部分を構成するものとする。   The bond represented by the general formula (4) is a silanol group and / or a hydrolyzable silyl group which the polysiloxane (a1) has, and a silanol group and / or a hydrolyzable silyl which the polymer (a2) has. It is generated by dehydration condensation reaction with a group. Accordingly, in the general formula (4), a carbon atom constitutes a part of the polymer (a2), and a silicon atom bonded only to an oxygen atom constitutes a part of the polysiloxane (a1).

前記複合樹脂（Ａ）中の前記ポリシロキサン（ａ１）は、７５〜９９質量％であることが重要であるが、より効果的に耐汚染性を付与することができることから、８０〜９８質量％であることが好ましく、８５〜９５質量％であることがより好ましい。   Although it is important that the polysiloxane (a1) in the composite resin (A) is 75 to 99% by mass, from the fact that the stain resistance can be more effectively imparted, 80 to 98% by mass Is preferably, and more preferably 85 to 95% by mass.

なお、前記ポリシロキサン（ａ１）の質量割合は、前記複合樹脂（Ａ）の製造に使用する原料の仕込み割合に基づき、加水分解縮合反応によって生成しうるメタノールやエタノール等の副生成物の生成を考慮し算出した値である。   The mass ratio of the polysiloxane (a1) is based on the preparation ratio of the raw materials used for the production of the composite resin (A), and the formation of by-products such as methanol and ethanol which can be generated by hydrolysis condensation reaction It is a value calculated taking into consideration.

前記ポリシロキサン（ａ１）は、ケイ素原子と酸素原子とからなる鎖状構造を有するものであって、加水分解性シリル基及び／又はシラノール基等を有するものである。   The polysiloxane (a1) has a chain structure composed of a silicon atom and an oxygen atom, and has a hydrolyzable silyl group and / or a silanol group.

前記加水分解性シリル基は、加水分解性基が前記ケイ素原子に直接結合した原子団であって、例えば、下記一般式（５）に示される構造からなるものである。   The hydrolyzable silyl group is an atomic group in which a hydrolyzable group is directly bonded to the silicon atom, and has, for example, a structure represented by the following general formula (5).

Figure 2019112488
（式中、Ｒ４はアルキル基、アリール基またはアラルキル基等の１価の有機基を、Ｒ５はハロゲン原子、アルコキシ基、アシロキシ基、フェノキシ基、アリールオキシ基、メルカプト基、アミノ基、アミド基、アミノオキシ基、イミノオキシ基またはアルケニルオキシ基である。また、ｎは０〜２の整数である。）
Figure 2019112488
 (Wherein R 4 is a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group, and R 5 is a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group, an amino group, an amide Group, aminooxy group, iminooxy group or alkenyloxy group, and n is an integer of 0 to 2.)

前記加水分解性基は、水の影響により水酸基を形成しうるものであって、例えば、ハロゲン原子、アルコキシ基、置換アルコキシ基、アシロキシ基、フェノキシ基、メルカプト基、アミノ基、アミド基、アミノオキシ基、イミノオキシ基、アルケニルオキシ基等が挙げられ、なかでもアルコキシ基や置換アルコキシ基であることが好ましい。   The hydrolyzable group is capable of forming a hydroxyl group under the influence of water, and includes, for example, a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, a mercapto group, an amino group, an amide group Groups, iminooxy groups, alkenyloxy groups and the like are mentioned, and among them, alkoxy groups and substituted alkoxy groups are preferable.

前記シラノール基は、水酸基が前記ケイ素原子に直接結合した原子団を示すものであって、前記加水分解性シリル基が加水分解した際に形成される。   The silanol group is an atomic group in which a hydroxyl group is directly bonded to the silicon atom, and is formed when the hydrolyzable silyl group is hydrolyzed.

前記ポリシロキサン（ａ１）は、保存安定性に優れ、効果的に耐汚染性を付与することができることから、前記一般式（１）又は（２）で表される構造単位（Ｕ１）を１０〜５５質量％有することが重要であるが、１０〜４０質量％有することがより好ましい。   The polysiloxane (a1) is excellent in storage stability and can effectively impart stain resistance, so that the structural unit (U1) represented by the general formula (1) or (2) is It is important to have 55% by mass, but it is more preferable to have 10 to 40% by mass.

また、前記ポリシロキサン（ａ１）は、効果的に耐汚染性を付与することができることから、前記一般式（３）で表される構造単位（Ｕ２）を１０質量％以上有することが重要であり、１５質量％以上有することが好ましい。   Moreover, since the said polysiloxane (a1) can provide stain resistance effectively, it is important to have 10 mass% or more of structural units (U2) represented by the said General formula (3). It is preferable to have 15 mass% or more.

前記ポリシロキサン（ａ１）は、前記構造単位（Ｕ１）、前記構造単位（Ｕ２）以外の構造単位として、例えば、下記一般式（６）又は（７）で表される構造単位（Ｕ３）等を有することができる。   The polysiloxane (a1) is a structural unit other than the structural unit (U1) and the structural unit (U2), for example, a structural unit (U3) represented by the following general formula (6) or (7), etc. It can have.

Figure 2019112488
Figure 2019112488

Figure 2019112488
（一般式（６）、（７）中のＲ６は芳香族炭化水素置換基以外の炭素原子数が３〜１２の有機基を表し、Ｒ７及びＲ８はそれぞれ独立してメチル基又はエチル基を表す。）
Figure 2019112488
 (R 6 in the general formulas (6) and (7) represents an organic group having 3 to 12 carbon atoms other than an aromatic hydrocarbon substituent, and R 7 and R 8 each independently represent a methyl group or an ethyl group Represents a group)

前記ポリシロキサン（ａ１）としては、例えば、後述するシラン化合物を完全にまたは部分的に加水分解縮合して得られるものを使用することができる。   As said polysiloxane (a1), what is obtained by carrying out the hydrolysis condensation of the silane compound mentioned later completely or partially can be used, for example.

前記ポリシロキサン（ａ１）の有する前記構造単位（Ｕ１）は、例えば、フェニルトリメトキシシラン、フェニルトリエトキシシラン、ジフェニルジメトキシシラン、メチルフェニルジメトキシシラン、フェニルトリクロロシラン、ジフェニルジクロロシラン等の芳香環を有するシラン化合物や、それらの部分加水分解縮合物などを使用することにより、前記ポリシロキサン（ａ１）中に容易に導入することができるが、これらの中でも、保存安定性に優れることから、フェニルトリメトキシシラン又はジフェニルジメトキシシランを使用することが好ましい。   The structural unit (U1) of the polysiloxane (a1) has, for example, an aromatic ring such as phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, phenyltrichlorosilane, diphenyldichlorosilane, etc. It can be easily introduced into the above-mentioned polysiloxane (a1) by using a silane compound, a partial hydrolytic condensate thereof or the like, but among these, phenyltrimethoxy is preferable because of its excellent storage stability. It is preferred to use silane or diphenyldimethoxysilane.

また、前記構造単位（Ｕ２）は、例えば、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリ−ｎ−ブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、メチルトリクロロシラン、エチルトリクロロシラン等のシラン化合物や、それらの部分加水分解縮合物などを使用することにより、前記ポリシロキサン（ａ１）中に容易に導入することができる。   The structural unit (U2) is, for example, a silane compound such as methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, methyltrichlorosilane, ethyltrichlorosilane, etc. And the partial hydrolysis condensates thereof can be easily introduced into the polysiloxane (a1).

また、前記構造単位（Ｕ３）は、例えば、ｎ−プロピルトリメトキシシラン、ｉｓｏ−ブチルトリメトキシシラン、シクロヘキシルトリメトキシシラン、ビニルトリメトキシシラン、３−（メタ）アクリロイルオキシプロピルトリメトキシシラン、３−（メタ）アクリロイルオキシプロピルトリエトキシシラン、３−（メタ）アクリロイルオキシプロピルトリクロロシラン、ビニルトリクロロシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジ−ｎ−ブトキシシラン、ジエチルジメトキシシラン、メチルシクロヘキシルジメトキシシラン、ジメチルジクロロシラン、ジエチルジクロロシラン等のシラン化合物や、それらの部分加水分解縮合物などを使用することにより、前記ポリシロキサン（ａ１）中に容易に導入することができる。   The structural unit (U3) is, for example, n-propyltrimethoxysilane, iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane, vinyltrimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (Meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltrichlorosilane, vinyltrichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, methylcyclohexyldimethoxysilane, It is easily introduced into the polysiloxane (a1) by using silane compounds such as dimethyldichlorosilane and diethyldichlorosilane, and partial hydrolytic condensates thereof. Rukoto can.

これらのシラン化合物は、単独で使用してもよいし、２種類以上の併用でもよい。   These silane compounds may be used alone or in combination of two or more.

前記重合体（ａ２）は、前記ポリシロキサン（ａ１）と反応しうる加水分解性シリル基及び／又はシラノール基を有するものである。   The polymer (a2) has a hydrolyzable silyl group and / or a silanol group capable of reacting with the polysiloxane (a1).

前記重合体（ａ２）としては、保存安定性に優れ、得られる塗膜の耐汚染性がより向上することから、３，０００〜１００，０００の数平均分子量を有するものを使用することが好ましく、５，０００〜２５，０００の数平均分子量を有するものを使用することがより好ましい。ここで、数平均分子量はゲル浸透クロマトグラフィー（以下、「ＧＰＣ」と略記する。）測定に基づきポリスチレン換算した値である。   As the polymer (a2), it is preferable to use one having a number average molecular weight of 3,000 to 100,000 because the storage stability is excellent and the stain resistance of the resulting coating film is further improved. It is more preferable to use one having a number average molecular weight of 5,000 to 25,000. Here, the number average molecular weight is a value converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement.

前記重合体（ａ２）としては、例えば、アクリル重合体、フルオロオレフィン重合体、ビニルエステル重合体、芳香族ビニル重合体等のビニル重合体；ポリエステル樹脂、アルキド樹脂、ポリウレタン樹脂などが挙げられるが、保存安定性に優れ、得られる塗膜の耐汚染性に優れることからビニル重合体が好ましい。   Examples of the polymer (a2) include vinyl polymers such as acrylic polymers, fluoroolefin polymers, vinyl ester polymers, and aromatic vinyl polymers; polyester resins, alkyd resins, polyurethane resins, etc. Vinyl polymers are preferred because they are excellent in storage stability and stain resistance of the resulting coating film.

前記ビニル重合体は、例えば、有機溶剤中、各種ビニル単量体を重合開始剤の存在下で重合することによって製造したものを使用することができる。   As the vinyl polymer, for example, those produced by polymerizing various vinyl monomers in an organic solvent in the presence of a polymerization initiator can be used.

前記加水分解性シリル基は、例えば、加水分解性シリル基を有するビニル単量体を重合することによって、前記ビニル重合体中に容易に導入することができる。   The hydrolyzable silyl group can be easily introduced into the vinyl polymer, for example, by polymerizing a vinyl monomer having a hydrolyzable silyl group.

前記加水分解性シリル基を有するビニル単量体としては、例えば、ビニルトリメトキシシラン、３−（メタ）アクリロイルオキシプロピルトリメトキシシラン、３−（メタ）アクリロイルオキシプロピルトリエトキシシランもしくは３−（メタ）アクリロイルオキシプロピルメチルジメトキシシラン等を使用することができ、なかでも、３−（メタ）アクリロイルオキシプロピルトリメトキシシランを使用することが好ましい。   Examples of the vinyl monomer having a hydrolyzable silyl group include vinyltrimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane or 3- (meth) Acryloyloxypropylmethyldimethoxysilane etc. can be used, and among them, it is preferable to use 3- (meth) acryloyloxypropyltrimethoxysilane.

前記加水分解性シリル基を有するビニル単量体以外の前記ビニル重合体の原料としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等の（メタ）アクリル酸エステル化合物；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、ポリエチレングリコール−ポリプロピレングリコール（メタ）アクリレート、グリセロールモノ（メタ）アクリレート等の水酸基を有するビニル単量体；メトキシポリエチレングリコール（メタ）アクリレート、エトキシポリエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、メトキシポリエチレングリコール−ポリプロピレングリコール（メタ）アクリレートフェノキシポリエチレングリコール−ポリプロピレングリコール（メタ）アクリレート等の末端がアルコキシ基又はフェノキシ基で封止されたポリオキシアルキレン基を有するビニル単量体；Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート等の三級アミノ基を有するビニル単量体；Ｎ−メチルアミノエチル（メタ）アクリレート等の二級アミノ基を有するビニル単量体；アミノメチルアクリレート等の一級アミノ基を有するビニル単量体等の塩基性窒素原子を有する基を有するビニル単量体；２，２，２−トリフルオロエチル（メタ）アクリレート等のフッ素原子を有するビニル単量体；酢酸ビニル等のビニルエステル化合物；メチルビニルエーテル等のビニルエーテル化合物；（メタ）アクリロニトリル等の不飽和カルボン酸のニトリル化合物；スチレン等の芳香族環を有するビニル化合物；イソプレン等のα−オレフィン化合物、グリシジル（メタ）アクリレート等のエポキシ基を有するビニル単量体；（メタ）アクリルアミド等のアミド基を有するビニル単量体；Ｎ−メチロール（メタ）アクリルアミド等のメチロールアミド基及びそのアルコキシ化物を有するビニル単量体；２−アジリジニルエチル（メタ）アクリレート等のアジリジニル基を有するビニル単量体；（メタ）アクリロイルイソシアナート等のイソシアナート基及び／またはブロック化イソシアナート基を有するビニル単量体；２−イソプロペニル−２−オキサゾリン等のオキサゾリン基を有するビニル単量体；ジシクロペンテニル（メタ）アクリレート等のシクロペンテニル基を有するビニル単量体；アクロレイン等のカルボニル基を有するビニル単量体；アセトアセトキシエチル（メタ）アクリレート等のアセトアセチル基を有するビニル単量体；（メタ）アクリル酸、イタコン酸、マレイン酸、もしくはこれらの半エステルまたはこれらの塩等のカルボキシル基を有する単量体などを使用することができる。   Examples of the raw material of the vinyl polymer other than the vinyl monomer having the hydrolyzable silyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) ) (Meth) acrylic acid ester compounds such as acrylate and cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate A vinyl monomer having a hydroxyl group such as acrylate), polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, glycerol mono (meth) acrylate; methoxypolyethylene Glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxy polyethylene glycol-polypropylene glycol (meth) acrylate phenoxy polyethylene glycol-polypropylene glycol (meth) acrylate Etc., a vinyl monomer having a polyoxyalkylene group in which the end is capped with an alkoxy group or a phenoxy group; a vinyl monomer having a tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate; -A vinyl monomer having a secondary amino group such as methylaminoethyl (meth) acrylate; a single monomer having a primary amino group such as aminomethyl acrylate Vinyl monomer having a group having a basic nitrogen atom such as; vinyl monomer having a fluorine atom such as 2,2,2-trifluoroethyl (meth) acrylate; vinyl ester compounds such as vinyl acetate; methyl vinyl ether Vinyl compounds such as (N); nitrile compounds of unsaturated carboxylic acids such as (meth) acrylonitrile; vinyl compounds having an aromatic ring such as styrene; α-olefin compounds such as isoprene; vinyl having an epoxy group such as glycidyl (meth) acrylate Monomers; vinyl monomers having an amide group such as (meth) acrylamide; methylolamide groups such as N-methylol (meth) acrylamide and vinyl monomers having an alkoxy compound thereof; 2-aziridinylethyl (meth) ) Vinyl monomers having an aziridinyl group such as acrylates; Ta) Vinyl monomer having isocyanate group such as acryloyl isocyanate and / or blocked isocyanate group; Vinyl monomer having oxazoline group such as 2-isopropenyl-2-oxazoline; Dicyclopentenyl (meth) Vinyl monomers having a cyclopentenyl group such as acrylates; vinyl monomers having a carbonyl group such as acrolein; vinyl monomers having an acetoacetyl group such as acetoacetoxyethyl (meth) acrylate; (meth) acrylic acid It is possible to use monomers having a carboxyl group such as itaconic acid, maleic acid or their half esters or their salts.

前記ビニル重合体を製造する際に使用可能な有機溶剤としては、例えば、ヘキサン、ヘプタン、オクタン、シクロヘキサン、シクロペンタン、シクロオクタン等の脂肪族系ないしは脂環族系の炭化水素化合物；トルエン、キシレンもしくはエチルベンゼン等の芳香族炭化水素化合物；酢酸エチル、酢酸ブチル、酢酸アミル、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート等のエステル化合物；メタノール、エタノール、ｎ−プロパノール、ｉ−プロパノール、ｎ−ブタノール、ｉ−ブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノール、ｎ−アミルアルコール、ｉ−アミルアルコール、ｔｅｒｔ−アミルアルコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル等のアルコール化合物；アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトン、シクロヘキサノン等のケトン化合物；ジメトキシエタン、テトラヒドロフラン、ジオキサン、ジイソプロピルエーテル、ジ−ｎ−ブチルエーテル等のエーテル化合物；クロロホルム、メチレンクロライド、四塩化炭素、トリクロロエタン、テトラクロロエタン等の塩素化炭化水素化合物；Ｎ−メチルピロリドン、ジメチルフォルムアミド、ジメチルアセトアミド、エチレンカーボネートなどを使用することができる。これらの有機溶剤は、単独で使用してもよいし、２種類以上の併用でもよい。   Examples of the organic solvent that can be used when producing the vinyl polymer include aliphatic or alicyclic hydrocarbon compounds such as hexane, heptane, octane, cyclohexane, cyclopentane, cyclooctane and the like; toluene, xylene Or an aromatic hydrocarbon compound such as ethylbenzene; ethyl acetate, butyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ester compound such as ethylene glycol monobutyl ether acetate; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, n-amyl alcohol, i-amyl alcohol, tert-amyl alcohol, ethylene Alcohol compounds such as recalled monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone and cyclohexanone; dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether, di-n -Ether compounds such as butyl ether; Chlorinated hydrocarbon compounds such as chloroform, methylene chloride, carbon tetrachloride, trichloroethane, tetrachloroethane, etc .; N-methylpyrrolidone, dimethyl formamide, dimethylacetamide, ethylene carbonate, etc. can be used. These organic solvents may be used alone or in combination of two or more.

前記ビニル重合体を製造する際に使用可能な重合開始剤としては、例えば、過硫酸塩、有機過酸化物、過酸化水素等のラジカル重合開始剤や、４，４’−アゾビス（４−シアノ吉草酸）、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩等のアゾ開始剤を使用することができる。また、前記ラジカル重合開始剤は、例えば、アスコルビン酸等の還元剤と併用しレドックス重合開始剤として使用してもよい。これらの重合開始剤は、単独で使用してもよいし、２種類以上の併用でもよい。   Examples of polymerization initiators that can be used when producing the vinyl polymer include, for example, radical polymerization initiators such as persulfates, organic peroxides and hydrogen peroxide, and 4,4′-azobis (4-cyano Azo initiators such as valeric acid), 2,2'-azobis (2-amidinopropane) dihydrochloride can be used. The radical polymerization initiator may be used as a redox polymerization initiator, for example, in combination with a reducing agent such as ascorbic acid. These polymerization initiators may be used alone or in combination of two or more.

前記重合開始剤の代表的なものである過硫酸塩としては、例えば、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等が挙げられ、有機過酸化物として、具体的には、例えば、過酸化ベンゾイル、ラウロイルパーオキサイド、デカノイルパーオキサイド等のジアシルパーオキサイド、ｔ−ブチルクミルパーオキサイド、ジクミルパーオキサイド等のジアルキルパーオキサイド、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシラウレート、ｔ−ブチルパーオキシベンゾエート等のパーオキシエステル、クメンハイドロパーオキサイド、パラメンタンハイドロパーオキサイド、ｔ−ブチルハイドロパーオキサイド等のハイドロパーオキサイド等を使用することができる。   Examples of the persulfate which is representative of the above-mentioned polymerization initiator include potassium persulfate, sodium persulfate, ammonium persulfate and the like, and as the organic peroxide, specifically, for example, benzoyl peroxide , Diacyl peroxides such as lauroyl peroxide and decanoyl peroxide, dialkyl peroxides such as t-butylcumyl peroxide and dicumyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxy Peroxy esters such as laurate, t-butylperoxybenzoate, cumene hydroperoxide, paramenthane hydroperoxide, hydroperoxides such as t-butyl hydroperoxide, etc. can be used.

重合開始剤の使用量は、重合が円滑に進行する量を使用すれば良いが、ビニル重合体（ａ２）の製造に使用するビニル単量体の全量に対して、１０質量％以下とすることが好ましい。   The amount of polymerization initiator used may be such that the polymerization proceeds smoothly, but should be 10% by mass or less based on the total amount of vinyl monomers used for producing the vinyl polymer (a2). Is preferred.

前記ビニル重合体のガラス転移温度は、保存安定性に優れ、耐汚染性がより向上することから、−５０〜９０℃の範囲内であることが好ましい。なお、本発明において、ガラス転移温度（Ｔｇ）とは、下記のＦＯＸの式で計算されるガラス転移温度をいう。
ＦＯＸの式：１／Ｔｇ＝Ｗ１／Ｔｇ１＋Ｗ２／Ｔｇ２＋・・・
（Ｔｇ：求めるべきガラス転移温度、Ｗ１：成分１の重量分率、Ｔｇ１：成分１のホモポリマーのガラス転移温度） The glass transition temperature of the vinyl polymer is preferably in the range of −50 to 90 ° C. because the storage stability is excellent and the stain resistance is further improved. In the present invention, the glass transition temperature (Tg) refers to the glass transition temperature calculated by the following formula of FOX.
Formula of FOX: 1 / Tg = W1 / Tg1 + W2 / Tg2 +.
(Tg: glass transition temperature to be determined, W1: weight fraction of component 1, Tg1: glass transition temperature of homopolymer of component 1)

また、前記ポリシロキサン（ａ１）は、前記複合樹脂（Ａ）を製造する工程において、２段階の反応工程を経ることによって形成することが好ましい。具体的には、前記ビニル重合体（ａ１）の有する加水分解性基等に、フェニルトリメトキシシラン等の比較的低分子量のシラン化合物を反応させることでポリシロキサン構造を形成し、次いで、該反応物と、メチルトリメトキシシランやエチルトリメトキシシラン等の縮合物とを反応させることによって、ポリシロキサン（ａ１）からなる構造を形成することができる。これにより、より一層、保存安定性に優れる耐汚染性付与剤を得ることができる。   Moreover, it is preferable to form the said polysiloxane (a1) by passing through a two-step reaction process in the process of manufacturing the said composite resin (A). Specifically, a polysiloxane structure is formed by reacting a relatively low molecular weight silane compound such as phenyltrimethoxysilane with the hydrolyzable group etc. possessed by the vinyl polymer (a1), and then the reaction By reacting a substance with a condensate such as methyltrimethoxysilane or ethyltrimethoxysilane, a structure composed of polysiloxane (a1) can be formed. Thereby, the contamination resistance imparting agent which is further excellent in storage stability can be obtained.

前記複合樹脂（Ａ）は、例えば、以下の（Ｉ）〜（ＩＩ）の工程によって製造することができる。   The composite resin (A) can be produced, for example, by the following steps (I) to (II).

（Ｉ）の工程は、有機溶剤中で、前記したビニル単量体を前記重合開始剤の存在下で重合することによってビニル重合体（ａ２）の有機溶剤溶液を得る工程である。   The step (I) is a step of polymerizing the above-mentioned vinyl monomer in the presence of the above-mentioned polymerization initiator in an organic solvent to obtain an organic solvent solution of the vinyl polymer (a2).

かかる重合反応は、例えば、重合開始剤を含む有機溶剤中に、前記ビニル単量体を逐次供給または一括供給し、次いで、攪拌下、２０〜１２０℃の範囲で０．５〜２４時間程度行うことが好ましい。   The polymerization reaction is carried out, for example, by sequentially feeding or batch feeding the vinyl monomer in an organic solvent containing a polymerization initiator, and then performing stirring for about 0.5 to 24 hours at a range of 20 to 120 ° C. Is preferred.

また、（ＩＩ）の工程は、前記ビニル重合体（ａ２）の有機溶剤溶液下で前記ビニル重合体（ａ２）の有する加水分解性シリル基等の反応性官能基と、シラン化合物の有する加水分解性シリル基またはシラノール基との反応と、前記シラン化合物間の加水分解縮合反応とを進行させることによって、前記ビニル重合体（ａ２）と前記ポリシロキサン（ａ１）とが結合した前記複合樹脂（Ａ）の有機溶剤溶液を得る工程である。   In the step (II), a reactive functional group such as a hydrolyzable silyl group possessed by the vinyl polymer (a2) in the organic solvent solution of the vinyl polymer (a2) and a hydrolysis possessed by the silane compound The composite resin (A) in which the vinyl polymer (a2) and the polysiloxane (a1) are bonded by advancing the reaction with a reactive silyl group or silanol group and the hydrolytic condensation reaction between the silane compounds A step of obtaining an organic solvent solution of

かかる反応は、例えば、（Ｉ）の工程に引き続き、前記ビニル重合体（ａ２）の有機溶剤溶液中に、前記ポリシロキサン（ａ１）を形成しうる前記シラン化合物を逐次供給または一括供給し、次いで、攪拌下、２０〜１２０℃の範囲で０．５〜２４時間程度行うことが好ましい。   Such reaction is carried out, for example, sequentially or collectively supplying the silane compound capable of forming the polysiloxane (a1) into the organic solvent solution of the vinyl polymer (a2) subsequently to the step (I). Under stirring, it is preferable to carry out in the range of 20 to 120 ° C. for about 0.5 to 24 hours.

（ＩＩ）の工程は、更に２段階の反応工程を経ることが好ましい。具体的には前記ビニル重合体（ａ２）の有する加水分解性シリル基またはシラノール基と、前記したフェニルトリメトキシシラン等の比較的低分子量のシラン化合物とを反応させる工程と、次いで、該反応物と、メチルトリメトキシシランやエチルトリメトキシシラン等のメチルトリアルコキシシラン及びエチルトリアルコキシシランを予め縮合させた縮合物とを反応させる工程とを経ることが好ましい。ポリシロキサン（ａ１）の構造形成を上記のような２段階で行うことで、一層、保存安定性に優れる耐汚染性付与剤を得ることができる。   The step (II) is preferably further subjected to two reaction steps. Specifically, the step of reacting the hydrolyzable silyl group or silanol group possessed by the vinyl polymer (a2) with a relatively low molecular weight silane compound such as the above-mentioned phenyltrimethoxysilane, and then the reaction product And a condensation product obtained by previously condensing methyltrialkoxysilane such as methyltrimethoxysilane or ethyltrimethoxysilane and ethyltrialkoxysilane. By performing the formation of the structure of the polysiloxane (a1) in the two steps as described above, a stain resistance imparting agent which is further excellent in storage stability can be obtained.

本発明の耐汚染性付与剤は、前記複合樹脂（Ａ）が、媒体中に溶解又は分散しているものであるが、前記媒体としては、例えば、前記ビニル重合体を製造する際に使用可能なものとして列挙した各種の有機溶剤等が挙げられる。   The stain resistance imparting agent of the present invention is one in which the composite resin (A) is dissolved or dispersed in a medium, and as the medium, for example, it can be used when producing the vinyl polymer And various organic solvents listed as examples.

本発明の耐汚染性付与剤は、保存安定性に優れ、効果的に各種材料の耐汚染性を向上できることから、コーティング剤等の各種用途に使用することができる。   Since the stain resistance imparting agent of the present invention is excellent in storage stability and can effectively improve the stain resistance of various materials, it can be used for various uses such as a coating agent.

本発明のコーティング剤は、前記耐汚染性付与剤を含有するものであるが、より耐汚染性に優れる硬化塗膜が得られることから、水性樹脂を含有することが好ましい。   The coating agent of the present invention contains the above-mentioned stain resistance imparting agent, but it is preferable to contain an aqueous resin because a cured coating film having more excellent stain resistance can be obtained.

前記水性樹脂としては、例えば、ビニル系樹脂、ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、エポキシエステル樹脂、アクリル樹脂、フェノール樹脂、石油樹脂、ケトン樹脂、シリコン樹脂、フッ素樹脂あるいはこれらの変性樹脂を使用することができる。これらの水性樹脂は、単独で使用してもよいし、２種類以上の併用でもよい。   As the aqueous resin, for example, vinyl resin, polyester resin, polyurethane resin, epoxy resin, epoxy ester resin, acrylic resin, phenol resin, petroleum resin, ketone resin, silicone resin, fluorine resin or modified resin thereof is used. be able to. These aqueous resins may be used alone or in combination of two or more.

前記コーティング剤中の前記耐汚染性付与剤の含有量としては、耐汚染性及びその他の塗膜物性のバランスがより向上することから、前記水性樹脂１００質量部に対し、０．０１〜５質量部の範囲が好ましい。   The content of the stain resistance imparting agent in the coating agent is 0.01 to 5 parts by mass with respect to 100 parts by mass of the water-based resin because the balance between the stain resistance and the other physical properties of the coating is further improved. A range of parts is preferred.

前記コーティング剤には、必要に応じて、前記水性樹脂の硬化剤を使用することができる。   As the coating agent, a curing agent of the aqueous resin can be used, if necessary.

前記コーティング剤には、必要に応じて粘土鉱物、金属、金属酸化物、ガラス等の各種の無機粒子を使用することができる。金属の種類としては、金、銀、銅、白金、チタン、亜鉛、ニッケル、アルミニウム、鉄、シリコン、ゲルマニウム、アンチモン、それらの金属酸化物等が挙げられる。   As the coating agent, various inorganic particles such as clay mineral, metal, metal oxide, glass and the like can be used as needed. Examples of metals include gold, silver, copper, platinum, titanium, zinc, nickel, aluminum, iron, silicon, germanium, antimony, metal oxides thereof, and the like.

前記コーティング剤には、必要に応じて光触媒性化合物や無機顔料、有機顔料、体質顔料、ワックス、界面活性剤、安定剤、流動調整剤、染料、レベリング剤、レオロジーコントロール剤、紫外線吸収剤、酸化防止剤、可塑剤等の各種の添加剤等を使用することができる。   The coating agent may, if necessary, be a photocatalytic compound, an inorganic pigment, an organic pigment, an extender pigment, a wax, a surfactant, a stabilizer, a flow control agent, a dye, a leveling agent, a rheology control agent, an ultraviolet absorber, oxidation Various additives such as an inhibitor and a plasticizer can be used.

前記コーティング剤を塗布し塗膜を形成可能な基材としては、例えば、無機質基材、金属基材、プラスチック基材、ガラス基材、紙や木材基材、繊維質基材等が挙げられる。   As a base material which can apply | coat the said coating agent and can form a coating film, an inorganic base material, a metal base material, a plastic base material, a glass base material, paper and a wood base material, a fibrous base material etc. are mentioned, for example.

前記基材上に、前記コーティング剤を塗装し、硬化させることによって、塗装物を得ることができる。その際に、（１）前記コーティング剤を基材に直接塗装する、（２）予め基材上に下塗り塗料を塗装してから、前記コーティング剤を上塗り塗料として塗装し塗膜を形成させる等の塗装方法により塗装物を得ることができる。   A coated article can be obtained by coating and curing the coating agent on the substrate. At that time, (1) apply the coating agent directly to the substrate, (2) apply an undercoat paint on the substrate beforehand, and then apply the coating agent as a top coat to form a coating film, etc. A paint can be obtained by the painting method.

前記コーティング剤を塗装する方法としては、例えば、刷毛塗り、ローラー塗装、スプレー塗装、浸漬塗装、フロー・コーター塗装、ロール・コーター塗装、電着塗装等が挙げられる。   Examples of the method for applying the coating agent include brush coating, roller coating, spray coating, dip coating, flow coater coating, roll coater coating, electrodeposition coating and the like.

また、前記（２）の塗装方法で前記コーティング剤からなる塗膜を有する塗装物を得る場合、下塗り塗料として、従来から知られているアクリル樹脂系塗料、ポリエステル樹脂系塗料、アルキド樹脂系塗料、エポキシ樹脂系塗料、脂肪酸変性エポキシ樹脂系塗料、シリコーン樹脂系塗料、ポリウレタン樹脂系塗料等を使用することができる。   Moreover, when obtaining the coated article which has a coating film which consists of the said coating agent by the coating method of said (2), the acrylic resin type paint conventionally known as an undercoat paint, a polyester resin type paint, an alkyd resin type paint, Epoxy resin based paints, fatty acid modified epoxy resin based paints, silicone resin based paints, polyurethane resin based paints, etc. can be used.

前記硬化を進行させる方法としては、常温下で１〜１０日程度養生する方法であってもよいが、硬化を迅速に進行させる観点から、５０〜２５０℃の温度で、１〜６００秒程度加熱する方法が好ましい。また、比較的高温で変形や変色をしやすいプラスチック基材を用いる場合には、３０〜１００℃程度の比較的低温下で養生を行うことが好ましい。   As a method of promoting the curing, it may be a method of curing for about 1 to 10 days under normal temperature, but from the viewpoint of rapidly promoting the curing, heating for about 1 to 600 seconds at a temperature of 50 to 250 ° C. Method is preferred. Moreover, when using the plastic base material which is comparatively high temperature and easy to deform | transform and discolor, it is preferable to harden under comparatively low temperature about 30-100 degreeC.

本発明のコーティング剤を用いて形成する塗膜の膜厚は、基材の使用される用途等に応じて、０．５〜１，０００μｍとすることができる。   The film thickness of the coating film formed using the coating agent of this invention can be 0.5-1,000 micrometers according to the use etc. in which the base material is used.

上記のような方法により、本発明のコーティング剤を用いて形成された塗膜を有する物品としては、例えば、外壁、屋根、ガラス、化粧板等の建築物の内外装材；防音壁、排水溝等の土木部材；テレビ、冷蔵庫、洗濯機、エアコン等の家電製品の筐体；パソコン、スマートフォン、携帯電話、デジタルカメラ、ゲーム機等の電子機器の筐体；プリンター、ファクシミリ等のＯＡ機器の筐体；自動車、鉄道車輌等の各種車輌の内外装材；産業機械等が挙げられる。   As an article having a coating film formed by using the coating agent of the present invention by the method as described above, for example, interior and exterior materials of buildings such as outer wall, roof, glass, decorative panel; soundproof wall, drainage ditch Civil engineering members such as: housings for home appliances such as TVs, refrigerators, washing machines, air conditioners; Housings for electronic devices such as personal computers, smart phones, mobile phones, digital cameras, game machines, etc. Housings for office automation equipment such as printers and facsimiles Body; interior and exterior materials of various vehicles such as automobiles and railway cars; industrial machines and the like.

次に、本発明を、実施例及び比較例により具体的に説明をする。なお、樹脂の平均分子量は、下記のＧＰＣ測定条件で測定したものである。   Next, the present invention will be specifically described by way of examples and comparative examples. In addition, the average molecular weight of resin is measured on the following GPC measurement conditions.

［ＧＰＣ測定条件］
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ−８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
「ＴＳＫｇｅｌ Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度４ｍｇ／ｍＬのテトラヒドロフラン溶液）
標準試料：下記の単分散ポリスチレンを用いて検量線を作成した。 [GPC measurement conditions]
Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were used in series connection.
"TSKgel G5000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 4000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 3000" (7.8 mm ID × 30 cm) × 1 This "TSKgel G2000" (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 4 mg / mL)
Standard sample: A calibration curve was prepared using the following monodispersed polystyrene.

（単分散ポリスチレン）
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−１０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−２５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ−５０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−１」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−２」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−４」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−１０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−２０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−４０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−８０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−１２８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−２８８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ−５５０」 (Monodispersed polystyrene)
Tosoh Corporation "TSKgel standard polystyrene A-500"
Tosoh Corporation "TSKgel standard polystyrene A-1000"
Tosoh Corporation "TSKgel standard polystyrene A-2500"
Tosoh Corporation "TSKgel standard polystyrene A-5000"
Tosoh Corporation "TSKgel standard polystyrene F-1"
Tosoh Corporation "TSKgel standard polystyrene F-2"
Tosoh Corporation "TSKgel standard polystyrene F-4"
Tosoh Corporation "TSKgel standard polystyrene F-10"
Tosoh Corporation "TSKgel standard polystyrene F-20"
Tosoh Corporation "TSKgel standard polystyrene F-40"
Tosoh Corporation "TSKgel standard polystyrene F-80"
Tosoh Corporation "TSKgel standard polystyrene F-128"
Tosoh Corporation "TSKgel standard polystyrene F-288"
Tosoh Corporation "TSKgel standard polystyrene F-550"

（合成例１：メチルトリメトキシシランの縮合物（ａ１’−１）の合成）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、メチルトリメトキシシラン（以下、「ＭＴＭＳ」と略記する。）１，４２１質量部を仕込んで、６０℃まで昇温した。次いで、前記反応容器中にｉｓｏ−プロピルアシッドホスフェート（ＳＣ有機化学株式会社製「Ｐｈｏｓｌｅｘ Ａ−３」）０．１７質量部と脱イオン水２０７質量部との混合物を５分間で滴下した後、８０℃の温度で４時間撹拌して加水分解縮合反応させた。
上記の加水分解縮合反応によって得られた縮合物を、温度４０〜６０℃及び４０〜１．３ｋＰａの減圧下（メタノールの留去開始時の減圧条件が４０ｋＰａで、最終的に１．３ｋＰａとなるまで減圧する条件をいう。以下、同様。）で蒸留し前記反応過程で生成したメタノール及び水を除去することによって、数平均分子量１，０００のＭＴＭＳの縮合物（ａ１’−１）を含有する液（有効成分７０質量％）１，０００質量部を得た。
なお、前記有効成分とは、ＭＴＭＳ等のシランモノマーのメトキシ基が全て縮合反応した場合の理論収量（質量部）を、縮合反応後の実収量（質量部）で除した値〔シランモノマーのメトキシ基が全て縮合反応した場合の理論収量（質量部）／縮合反応後の実収量（質量部）〕により算出したものである。 Synthesis Example 1: Synthesis of methyltrimethoxysilane condensate (a1′-1)
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling pipe and nitrogen gas inlet, 1,421 parts by mass of methyltrimethoxysilane (hereinafter abbreviated as "MTMS") was charged, and the temperature was raised to 60 ° C. It warmed. Then, a mixture of 0.17 parts by mass of iso-propyl acid phosphate ("Phoslex A-3" manufactured by SC Organic Chemical Co., Ltd.) and 207 parts by mass of deionized water is dropped into the reaction vessel over 5 minutes, and then 80 The mixture was stirred at a temperature of ° C for 4 hours for hydrolysis and condensation reaction.
The condensate obtained by the above hydrolysis condensation reaction is reduced in temperature at 40 to 60 ° C. and 40 to 1.3 kPa (the reduced pressure condition at the start of distillation of methanol is 40 kPa and finally it becomes 1.3 kPa) Refers to the conditions under which the pressure is reduced down to the following: Same as above) and removes methanol and water generated in the reaction process, thereby containing MTMS condensate (a1'-1) with a number average molecular weight of 1,000. 1,000 parts by mass of liquid (70% by mass of active ingredient) was obtained.
The above-mentioned effective ingredient is the value obtained by dividing the theoretical yield (parts by mass) when all the methoxy groups of silane monomers such as MTMS are condensation reacted by the actual yield (parts by mass) after the condensation reaction [methoxy of silane monomer It is calculated by the theoretical yield (mass part) / real yield after condensation reaction (mass part)] when all the groups carry out a condensation reaction.

（実施例１：耐汚染性付与剤（１）の製造）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、ｎ−ブタノール（以下、「ＢｕＯＨ」と略記する。）１５０質量部、フェニルトリメトキシシラン（以下、「ＰＴＭＳ」と略記する。）８８質量部、ジメチルジメトキシシラン（以下、「ＤＭＤＭＳ」と略記する。）２３３質量部を仕込んで８０℃まで昇温した。
次いで、同温度でメチルメタクリレート（以下、「ＭＭＡ」と略記する。）８４質量部、ブチルメタクリレート（以下、「ＢＭＡ」と略記する。）１６質量部、ブチルアクリレート（以下、「ＢＡ」と略記する。）１３質量部、３−メタクリルオキシプロピルトリメトキシシラン（以下、「ＭＰＴＳ」と略記する。）７質量部、ＢｕＯＨ１２質量部及びｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート（以下、「ＴＢＰＥＨ」と略記する。）２．４質量部を含有する混合物を、前記反応容器中へ４時間で滴下し、滴下終了後、更に同温度で２０時間反応させて加水分解性シリル基を有する数平均分子量が１０，２００のビニル重合体（ａ２−１）の有機溶剤溶液を得た。
次いで、ｉｓｏ−プロピルアシッドホスフェート（ＳＣ有機化学株式会社製「Ｐｈｏｓｌｅｘ Ａ−３」、以下「Ａ−３」と略記する。）０．０４質量部と脱イオン水９４質量部との混合物を、５分間で滴下し、更に同温度で１０時間攪拌して加水分解縮合反応させることで、ビニル重合体（ａ２−１）の有する加水分解性シリル基と、前記ＰＴＭＳ及びＤＭＤＭＳ由来のポリシロキサンの有する加水分解性シリル基及びシラノール基とが結合した複合樹脂を含有する液を得た。
次いで、この液に合成例１で得られたＭＴＭＳの縮合物（ａ１’−１）３９８質量部、脱イオン水 ６７質量部を添加し、同温度で１０時間攪拌して加水分解縮合反応させたものを、合成例１と同様の条件で蒸留することによって生成したメタノール及び水を除去し、次いで、ＢｕＯＨ ２５０質量部を添加し、不揮発分が６０．１質量％の耐汚染性付与剤（１）を１，０００質量部得た。 (Example 1: Production of stain resistance imparting agent (1))
150 parts by mass of n-butanol (hereinafter abbreviated as "BuOH"), phenyltrimethoxysilane (hereinafter "PTMS") in a reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling pipe and nitrogen gas inlet 88 parts by mass, and 233 parts by mass of dimethyldimethoxysilane (hereinafter abbreviated as "DMDMS") were charged, and the temperature was raised to 80.degree.
Subsequently, 84 parts by mass of methyl methacrylate (hereinafter abbreviated as "MMA"), 16 parts by mass of butyl methacrylate (hereinafter abbreviated as "BMA") at the same temperature, and butyl acrylate (hereinafter abbreviated as "BA") ) 13 parts by mass, 7 parts by mass of 3-methacryloxypropyltrimethoxysilane (hereinafter abbreviated as "MPTS"), 12 parts by mass of BuOH and tert-butylperoxy-2-ethylhexanoate (hereinafter "TBPEH") A mixture containing 2.4 parts by mass is dropped into the reaction vessel over 4 hours, and after completion of the dropping, the mixture is further reacted at the same temperature for 20 hours to obtain a number average having a hydrolyzable silyl group. An organic solvent solution of vinyl polymer (a2-1) having a molecular weight of 10,200 was obtained.
Then, a mixture of 0.04 parts by mass of iso-propyl acid phosphate ("Phoslex A-3" manufactured by SC Organic Chemical Co., Ltd., hereinafter abbreviated as "A-3") and 94 parts by mass of deionized water is The reaction solution is added dropwise for 1 minute, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, whereby the hydrolysis of the hydrolyzable silyl group possessed by the vinyl polymer (a2-1) and the hydrolysis possessed by the PTMS and DMMS derived from polysiloxane. A liquid containing a composite resin in which a degradable silyl group and a silanol group were bonded was obtained.
Next, 398 parts by mass of the MTMS condensate (a1′-1) obtained in Synthesis Example 1 and 67 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction. The product is distilled under the same conditions as in Synthesis Example 1 to remove methanol and water, and then 250 parts by mass of BuOH is added, and a non-volatile component is 60.1% by mass of a stain resistance imparting agent (1 1,000 parts by mass was obtained.

（実施例２：耐汚染性付与剤（２）の製造）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、ＢｕＯＨ １５０質量部、ＰＴＭＳ ９９質量部、ＤＭＤＭＳ ２６３質量部を仕込んで８０℃まで昇温した。
次いで、同温度でＭＭＡ ４２質量部、ＢＭＡ ８質量部、ＢＡ ７質量部、ＭＰＴＳ ４質量部、ＢｕＯＨ ６質量部及びＴＢＰＥＨ １．２質量部を含有する混合物を、前記反応容器中へ５時間で滴下し、滴下終了後、更に同温度で２０時間反応させて加水分解性シリル基を有する数平均分子量が１０，３００のビニル重合体（ａ２−２）の有機溶剤溶液を得た。
次いで、Ａ−３ ０．０４質量部と脱イオン水 １０６質量部との混合物を、５分間で滴下し、更に同温度で１０時間攪拌して加水分解縮合反応させることで、ビニル重合体（ａ２−２）の有する加水分解性シリル基と、前記ＰＴＭＳ及びＤＭＤＭＳ由来のポリシロキサンの有する加水分解性シリル基及びシラノール基とが結合した複合樹脂を含有する液を得た。
次いで、この液に合成例１で得られたＭＴＭＳの縮合物（ａ１’−１）４４７質量部、脱イオン水 ７６質量部を添加し、同温度で１０時間攪拌して加水分解縮合反応させたものを、合成例１と同様の条件で蒸留することによって生成したメタノール及び水を除去し、次いで、ＢｕＯＨ ２５０質量部を添加し、不揮発分が６０．０質量％の耐汚染性付与剤（２）を１，０００質量部得た。 (Example 2: Production of stain resistance imparting agent (2))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 99 parts by mass of PTMS and 263 parts by mass of DMDS were charged, and the temperature was raised to 80 ° C.
Then, a mixture containing 42 parts by mass of MMA, 8 parts by mass of BMA, 7 parts by mass of BA, 4 parts by mass of MPTS, 6 parts by mass of BuOH and 1.2 parts by mass of TBPEH at the same temperature for 5 hours into the reaction vessel It dripped and it made it react at the same temperature for 20 hours after completion | finish of dripping, and obtained the organic solvent solution of the vinyl polymer (a2-2) of the number average molecular weight 10,300 which has a hydrolysable silyl group.
Next, a mixture of 0.04 parts by mass of A-3 and 106 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group possessed by (-2) and the hydrolyzable silyl group and silanol group possessed by the PTMS and the DMMS derived from polysiloxane are bonded.
Next, 447 parts by mass of the MTMS condensate (a1'-1) obtained in Synthesis Example 1 and 76 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction. The product is distilled under the same conditions as in Synthesis Example 1 to remove methanol and water, and then 250 parts by mass of BuOH is added, and a non-volatile content is 60.0% by mass. 1,000 parts by mass was obtained.

（実施例３：耐汚染性付与剤（３）の製造）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、ＢｕＯＨ １５０質量部、ＰＴＭＳ １０５質量部、ＤＭＤＭＳ ２７７質量部を仕込んで８０℃まで昇温した。
次いで、同温度でＭＭＡ ２１質量部、ＢＭＡ ４質量部、ＢＡ ３質量部、ＭＰＴＳ ２質量部、ＢｕＯＨ ３質量部及びＴＢＰＥＨ ０．６質量部を含有する混合物を、前記反応容器中へ６時間で滴下し、滴下終了後、更に同温度で２０時間反応させて加水分解性シリル基を有する数平均分子量が１０，０００のビニル重合体（ａ２−３）の有機溶剤溶液を得た。
次いで、Ａ−３ ０．０４質量部と脱イオン水 １１２質量部との混合物を、５分間で滴下し、更に同温度で１０時間攪拌して加水分解縮合反応させることで、ビニル重合体（ａ２−３）の有する加水分解性シリル基と、前記ＰＴＭＳ及びＤＭＤＭＳ由来のポリシロキサンの有する加水分解性シリル基及びシラノール基とが結合した複合樹脂を含有する液を得た。
次いで、この液に合成例１で得られたＭＴＭＳの縮合物（ａ１’−１）４７２質量部、脱イオン水 ８０質量部を添加し、同温度で１０時間攪拌して加水分解縮合反応させたものを、合成例１と同様の条件で蒸留することによって生成したメタノール及び水を除去し、次いで、ＢｕＯＨ ２５０質量部を添加し、不揮発分が６０．１質量％の耐汚染性付与剤（３）を１，０００質量部得た。 (Example 3: Production of stain resistance imparting agent (3))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 105 parts by mass of PTMS and 277 parts by mass of DMDS were charged, and the temperature was raised to 80 ° C.
Then, a mixture containing 21 parts by mass of MMA, 4 parts by mass of BMA, 3 parts by mass of BA, 2 parts by mass of MPTS, 3 parts by mass of BuOH and 0.6 parts by mass of TBPEH at the same temperature for 6 hours into the reaction vessel It dripped and it made it react at the same temperature for 20 hours after completion | finish of dripping, and obtained the organic solvent solution of the vinyl polymer (a2-3) of the number average molecular weight 10,000 which has a hydrolysable silyl group.
Next, a mixture of 0.04 parts by mass of A-3 and 112 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group of -3) and the hydrolyzable silyl group and silanol group of the PTMS and the polysiloxane derived from DMMS are bonded.
Next, to this solution, 472 parts by mass of the MTMS condensate (a1′-1) obtained in Synthesis Example 1 and 80 parts by mass of deionized water were added, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction. The product is distilled under the same conditions as in Synthesis Example 1 to remove methanol and water, and then 250 parts by mass of BuOH is added, and a non-volatile component is 60.1% by mass of a stain resistance imparting agent (3 1,000 parts by mass was obtained.

（実施例４：耐汚染性付与剤（４）の製造）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、ＢｕＯＨ １５０質量部、ＰＴＭＳ １０８質量部、ＤＭＤＭＳ ２８６質量部を仕込んで８０℃まで昇温した。
次いで、同温度でＭＭＡ ８質量部、ＢＭＡ ２質量部、ＢＡ １質量部、ＭＰＴＳ １質量部、ＢｕＯＨ ２質量部及びＴＢＰＥＨ ０．３質量部を含有する混合物を、前記反応容器中へ６時間で滴下し、滴下終了後、更に同温度で２０時間反応させて加水分解性シリル基を有する数平均分子量が１０，３００のビニル重合体（ａ２−４）の有機溶剤溶液を得た。
次いで、Ａ−３ ０．０５質量部と脱イオン水 １１５質量部との混合物を、５分間で滴下し、更に同温度で１０時間攪拌して加水分解縮合反応させることで、ビニル重合体（ａ２−４）の有する加水分解性シリル基と、前記ＰＴＭＳ及びＤＭＤＭＳ由来のポリシロキサンの有する加水分解性シリル基及びシラノール基とが結合した複合樹脂を含有する液を得た。
次いで、この液に合成例１で得られたＭＴＭＳの縮合物（ａ１’−１）４８７質量部、脱イオン水 ８２質量部を添加し、同温度で１０時間攪拌して加水分解縮合反応させたものを、合成例１と同様の条件で蒸留することによって生成したメタノール及び水を除去し、次いで、ＢｕＯＨ ２５０質量部を添加し、不揮発分が６０．２質量％の耐汚染性付与剤（４）を１，０００質量部得た。 (Example 4: Production of stain resistance imparting agent (4))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 108 parts by mass of PTMS and 286 parts by mass of DMDMS were charged and the temperature was raised to 80 ° C.
Then, a mixture containing 8 parts by mass of MMA, 2 parts by mass of BMA, 1 part by mass of BA, 1 part by mass of MPTS, 2 parts by mass of BuOH and 0.3 parts by mass of TBPEH at the same temperature for 6 hours into the reaction vessel It dripped and it made it react at the same temperature for 20 hours after completion | finish of dripping, and obtained the organic solvent solution of the vinyl polymer (a2-4) of the number average molecular weight 10,300 which has a hydrolysable silyl group.
Next, a mixture of 0.05 parts by mass of A-3 and 115 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group possessed by (4) and the hydrolyzable silyl group possessed by the PTMS and the polysiloxane derived from DMDMS and the silanol group are bonded.
Next, 487 parts by mass of the MTMS condensate (a1'-1) obtained in Synthesis Example 1 and 82 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction. The product is distilled under the same conditions as in Synthesis Example 1 to remove methanol and water, and then 250 parts by mass of BuOH is added, and a non-volatile content is 60.2% by mass of a stain resistance imparting agent (4 1,000 parts by mass was obtained.

（実施例５：耐汚染性付与剤（５）の製造）
実施例２で使用した、ＭＭＡ ４２質量部、ＢＭＡ ８質量部、ＢＡ ７質量部、ＭＰＴＳ ４質量部、ＢｕＯＨ ６質量部及びＴＢＰＥＨ １．２質量部を含有する混合物の代わりに、ＭＭＡ １８質量部、ＢＭＡ １４質量部、ＢＡ ７質量部、アクリル酸（以下、「ＡＡ」と略記する。）１質量部、ＭＰＴＳ ２質量部、ＢｕＯＨ ６質量部及びＴＢＰＥＨ ０．９質量部を含有する混合物を使用した以外は、実施例２と同様の操作を行い、不揮発分が６０．０％の耐汚染性付与剤（５）を１，０００質量部得た。 (Example 5: Production of stain resistance imparting agent (5))
MMA 18 parts by weight instead of the mixture used in Example 2 containing 42 parts by weight of MMA, 8 parts by weight of BMA, 7 parts by weight of BA, 4 parts by weight of MPTS, 6 parts by weight of BuOH and 1.2 parts by weight of TBPEH , BMA 14 parts by mass, BA 7 parts by mass, acrylic acid (hereinafter abbreviated as “AA”) 1 part by mass, MPTS 2 parts by mass, BuOH 6 parts by mass and TBPEH 0.9 parts by mass. An operation was performed in the same manner as in Example 2 except for the above to obtain 1,000 parts by mass of a stain resistance imparting agent (5) having a nonvolatile content of 60.0%.

（実施例６：耐汚染性付与剤（６）の製造）
実施例２で使用した、ＭＭＡ ４２質量部、ＢＭＡ ８質量部、ＢＡ ７質量部、ＭＰＴＳ ４質量部、ＢｕＯＨ ６質量部及びＴＢＰＥＨ １．２質量部を含有する混合物の代わりに、ＭＭＡ １２質量部、シクロヘキシルメタクリレート １５質量部、２−エチルヘキシルアクリレート ３２質量部、ＭＰＴＳ １質量部、ＢｕＯＨ ６質量部及びＴＢＰＥＨ ０．６質量部を含有する混合物を使用した以外は、実施例２と同様の操作を行ない、不揮発分が６０．２％の耐汚染性付与剤（６）を１，０００質量部得た。 (Example 6: Production of stain resistance imparting agent (6))
MMA 12 parts by mass instead of the mixture used in Example 2 containing 42 parts by mass of MMA, 8 parts by mass of BMA, 7 parts by mass of BA, 4 parts by mass of MPTS, 6 parts by mass of BuOH and 1.2 parts by mass of TBPEH The procedure of Example 2 is repeated except that a mixture containing 15 parts by mass of cyclohexyl methacrylate, 32 parts by mass of 2-ethylhexyl acrylate, 1 part by mass of MPTS, 6 parts by mass of BuOH and 0.6 parts by mass of TBPEH is used. And 1,000 parts by mass of a stain resistance imparting agent (6) having a nonvolatile content of 60.2%.

（実施例７：耐汚染性付与剤（７）の製造）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、ＢｕＯＨ １５０質量部、ジフェニルジメトキシシラン（以下、「ＤＰＤＭＳ」と略記する。）１３３質量部、ＤＭＤＭＳ ３５０質量部を仕込んで８０℃まで昇温した。
次いで、同温度でＭＭＡ １８質量部、ＢＭＡ １４質量部、ＢＡ ７質量部、ＡＡ １質量部、ＭＰＴＳ ２質量部、ＢｕＯＨ ６質量部及びＴＢＰＥＨ ０．９質量部を含有する混合物を、前記反応容器中へ５時間で滴下し、滴下終了後、更に同温度で１０時間反応させて加水分解性シリル基を有する数平均分子量が２０，０００のビニル重合体（ａ２−７）の有機溶剤溶液を得た。
次いで、Ａ−３ ０．０５質量部と脱イオン水 １３４質量部との混合物を、５分間で滴下し、更に同温度で１０時間攪拌して加水分解縮合反応させることで、ビニル重合体（ａ２−７）の有する加水分解性シリル基と、前記ＤＰＤＭＳ及びＤＭＤＭＳ由来のポリシロキサンの有する加水分解性シリル基及びシラノール基とが結合した複合樹脂を含有する液を得た。
次いで、この液に合成例１で得られたＭＴＭＳの縮合物（ａ１’−１）３０９質量部、脱イオン水 ５２質量部を添加し、同温度で１５時間攪拌して加水分解縮合反応させたものを、合成例１と同様の条件で蒸留することによって生成したメタノール及び水を除去し、次いで、ＢｕＯＨ ２５０質量部を添加し、不揮発分が６０．０質量％の耐汚染性付与剤（７）を１，０００質量部得た。 (Example 7: Production of stain resistance imparting agent (7))
150 parts by mass of BuOH, 133 parts by mass of diphenyldimethoxysilane (hereinafter abbreviated as "DPDMS"), and 350 parts by mass of DMDMS in a reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling pipe and nitrogen gas inlet The mixture was charged and heated to 80 ° C.
Subsequently, a mixture containing 18 parts by mass of MMA, 14 parts by mass of BMA, 7 parts by mass of BA, 1 part by mass of AA, 2 parts by mass of MPTS, 6 parts by mass of BuOH and 0.9 parts by mass of TBPEH at the same temperature The reaction solution is dropped for 5 hours and allowed to react at the same temperature for 10 hours to obtain an organic solvent solution of a vinyl polymer (a2-7) having a hydrolyzable silyl group and having a number average molecular weight of 20,000. The
Next, a mixture of 0.05 parts by mass of A-3 and 134 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 A liquid containing a composite resin in which the hydrolyzable silyl group possessed by (7) and the hydrolyzable silyl group possessed by the DDPMS and the polysiloxane derived from DMDMS and the silanol group are bonded is obtained.
Next, 309 parts by mass of the MTMS condensate (a1′-1) obtained in Synthesis Example 1 and 52 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 15 hours to cause a hydrolysis condensation reaction. The product is distilled under the same conditions as in Synthesis Example 1 to remove methanol and water generated, and then 250 parts by mass of BuOH is added, and a non-volatile content is 60.0% by mass. 1,000 parts by mass was obtained.

（実施例８：耐汚染性付与剤（８）の製造）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、ＢｕＯＨ １５０質量部、ＰＴＭＳ ２４９質量部、ＤＭＤＭＳ ２６３質量部を仕込んで８０℃まで昇温した。
次いで、同温度でＭＭＡ １８質量部、ＢＭＡ １４質量部、ＢＡ ７質量部、ＡＡ １質量部、ＭＰＴＳ ２質量部、ＢｕＯＨ ６質量部及びＴＢＰＥＨ ０．９質量部を含有する混合物を、前記反応容器中へ５時間で滴下し、滴下終了後、更に同温度で１０時間反応させて加水分解性シリル基を有する数平均分子量が２０，１００のビニル重合体（ａ２−８）の有機溶剤溶液を得た。
次いで、Ａ−３ ０．０５質量部と脱イオン水 １４７質量部との混合物を、５分間で滴下し、更に同温度で１０時間攪拌して加水分解縮合反応させることで、ビニル重合体（ａ２−８）の有する加水分解性シリル基と、前記ＰＴＭＳ及びＤＭＤＭＳ由来のポリシロキサンの有する加水分解性シリル基及びシラノール基とが結合した複合樹脂を含有する液を得た。
次いで、この液に３−グリシドキシプロピルトリメトキシシラン ７６質量部、合成例１で得られたＭＴＭＳの縮合物（ａ１’−１）２３１質量部、脱イオン水 ５６質量部を添加し、同温度で１５時間攪拌して加水分解縮合反応させたものを、合成例１と同様の条件で蒸留することによって生成したメタノール及び水を除去し、次いで、ＢｕＯＨ ２５０質量部を添加し、不揮発分が６０．０質量％の耐汚染性付与剤（８）を１，０００質量部得た。 (Example 8: Production of stain resistance imparting agent (8))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser and a nitrogen gas inlet, 150 parts by mass of BuOH, 249 parts by mass of PTMS and 263 parts by mass of DMDS were charged, and the temperature was raised to 80 ° C.
Subsequently, a mixture containing 18 parts by mass of MMA, 14 parts by mass of BMA, 7 parts by mass of BA, 1 part by mass of AA, 2 parts by mass of MPTS, 6 parts by mass of BuOH and 0.9 parts by mass of TBPEH at the same temperature The reaction solution is dropped for 5 hours into the mixture, and after completion of the dropping, the mixture is further reacted at the same temperature for 10 hours to obtain an organic solvent solution of a vinyl polymer (a2-8) having a hydrolyzable silyl group and a number average molecular weight of 20,100 The
Next, a mixture of 0.05 parts by mass of A-3 and 147 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group possessed by -8) and the hydrolyzable silyl group possessed by the PTMS and the DMMS derived from polysiloxane and the silanol group are bonded.
Subsequently, 76 parts by mass of 3-glycidoxypropyltrimethoxysilane, 231 parts by mass of the MTMS condensate (a1'-1) obtained in Synthesis Example 1, and 56 parts by mass of deionized water are added to this solution, Methanol and water which were produced by distilling under the same conditions as those of Synthesis Example 1 were removed by stirring at a temperature for 15 hours for hydrolysis and condensation reaction, then 250 parts by mass of BuOH was added, and the non volatile matter was 1,000 parts by mass of 60.0% by mass of the stain resistance imparting agent (8) was obtained.

（実施例９：耐汚染性付与剤（９）の製造）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、ＢｕＯＨ １５０質量部、ＰＴＭＳ ４１４質量部、ＤＭＤＭＳ ２６３質量部を仕込んで８０℃まで昇温した。
次いで、同温度でＭＭＡ １８質量部、ＢＭＡ １４質量部、ＢＡ ７質量部、ＡＡ １質量部、ＭＰＴＳ ２質量部、ＢｕＯＨ ６質量部及びＴＢＰＥＨ ０．９質量部を含有する混合物を、前記反応容器中へ６時間で滴下し、滴下終了後、更に同温度で１０時間反応させて加水分解性シリル基を有する数平均分子量が１９，６００のビニル重合体（ａ２−９）の有機溶剤溶液を得た。
次いで、Ａ−３ ０．０７質量部と脱イオン水 １９２質量部との混合物を、５分間で滴下し、更に同温度で１０時間攪拌して加水分解縮合反応させることで、ビニル重合体（ａ２−９）の有する加水分解性シリル基と、前記ＰＴＭＳ及びＤＭＤＭＳ由来のポリシロキサンの有する加水分解性シリル基及びシラノール基とが結合した複合樹脂を含有する液を得た。
次いで、この液に合成例１で得られたＭＴＭＳの縮合物（ａ１’−１）１５４質量部、脱イオン水 ２６質量部を添加し、同温度で５時間攪拌して加水分解縮合反応させたものを、合成例１と同様の条件で蒸留することによって生成したメタノール及び水を除去し、次いで、ＢｕＯＨ ２５０質量部を添加し、不揮発分が６０．１質量％の耐汚染性付与剤（９）を１，０００質量部得た。 (Example 9: Production of stain resistance imparting agent (9))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser and a nitrogen gas inlet, 150 parts by mass of BuOH, 414 parts by mass of PTMS and 263 parts by mass of DMDMS were charged and the temperature was raised to 80 ° C.
Subsequently, a mixture containing 18 parts by mass of MMA, 14 parts by mass of BMA, 7 parts by mass of BA, 1 part by mass of AA, 2 parts by mass of MPTS, 6 parts by mass of BuOH and 0.9 parts by mass of TBPEH at the same temperature The reaction solution is dropped for 6 hours, and after completion of the dropwise addition, the reaction is carried out for 10 hours at the same temperature to obtain an organic solvent solution of a vinyl polymer (a2-9) having a hydrolyzable silyl group and a number average molecular weight of 19,600. The
Next, a mixture of 0.07 parts by mass of A-3 and 192 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, whereby a vinyl polymer (a2 There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group of -9) and the hydrolyzable silyl group and silanol group of the PTMS and the polysiloxane derived from DMMS are bonded.
Next, 154 parts by mass of the MTMS condensate (a1'-1) obtained in Synthesis Example 1 and 26 parts by mass of deionized water were added to this solution, and the mixture was stirred for 5 hours at the same temperature to cause a hydrolysis condensation reaction. The product is distilled under the same conditions as in Synthesis Example 1 to remove methanol and water, and then 250 parts by mass of BuOH is added, and a non-volatile component is 60.1% by mass of a stain resistance imparting agent (9 1,000 parts by mass was obtained.

（比較例１：比較用樹脂組成物（Ｒ１）の製造）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、ＢｕＯＨ １５０質量部、ＰＴＭＳ ３３質量部、ＤＭＤＭＳ ８８質量部を仕込んで８０℃まで昇温した。
次いで、同温度でＭＭＡ ２９４質量部、ＢＭＡ ５５質量部、ＢＡ ４６質量部、ＭＰＴＳ ２５質量部、ＢｕＯＨ ４２質量部及びＴＢＰＥＨ ８．４質量部を含有する混合物を、前記反応容器中へ３時間で滴下し、滴下終了後、更に同温度で２０時間反応させて加水分解性シリル基を有する数平均分子量が１１，０００のビニル重合体（Ｒａ２−１）の有機溶剤溶液を得た。
次いで、Ａ−３ ０．０１質量部と脱イオン水 ３５質量部との混合物を、５分間で滴下し、更に同温度で１０時間攪拌して加水分解縮合反応させることで、ビニル重合体（Ｒａ２−１）の有する加水分解性シリル基と、前記ＰＴＭＳ及びＤＭＤＭＳ由来のポリシロキサンの有する加水分解性シリル基及びシラノール基とが結合した複合樹脂を含有する液を得た。
次いで、この液に合成例１で得られたＭＴＭＳの縮合物（ａ１’−１）１４９質量部、脱イオン水 ２５質量部を添加し、同温度で１０時間攪拌して加水分解縮合反応させたものを、合成例１と同様の条件で蒸留することによって生成したメタノール及び水を除去し、次いで、ＢｕＯＨ ２５０質量部を添加し、不揮発分が６０．０質量％の比較用樹脂組成物（Ｒ１）を１，０００質量部得た。 Comparative Example 1: Production of Comparative Resin Composition (R1)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 33 parts by mass of PTMS, and 88 parts by mass of DMDMS were charged and the temperature was raised to 80 ° C.
Then, at the same temperature, a mixture containing 294 parts by mass of MMA, 55 parts by mass of BMA, 46 parts by mass of BA, 25 parts by mass of MPTS, 42 parts by mass of BuOH and 8.4 parts by mass of TBPEH is introduced into the reaction vessel for 3 hours It dripped and it made it react at the same temperature for 20 hours after completion | finish of dripping, and obtained the organic solvent solution of the vinyl polymer (Ra2-1) of the number average molecular weight 11,000 which has a hydrolysable silyl group.
Next, a mixture of 0.01 part by mass of A-3 and 35 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, thereby obtaining a vinyl polymer (Ra2). There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group possessed by -1) and the hydrolyzable silyl group possessed by the PTMS and the DMMS derived from polysiloxane and the silanol group are bonded.
Subsequently, 149 parts by mass of the MTMS condensate (a1'-1) obtained in Synthesis Example 1 and 25 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction. The product was subjected to distillation under the same conditions as in Synthesis Example 1 to remove methanol and water generated, and then 250 parts by mass of BuOH was added, and a resin composition for comparison (R1 having a nonvolatile content of 60.0% by mass) 1,000 parts by mass was obtained.

（比較例２：比較用樹脂組成物（Ｒ２）の製造）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、ＢｕＯＨ １５０質量部、ＰＴＭＳ ６６質量部、ＤＭＤＭＳ １７５質量部を仕込んで８０℃まで昇温した。
次いで、同温度でＭＭＡ １６８質量部、ＢＭＡ ３１質量部、ＢＡ ２６質量部、ＭＰＴＳ １４質量部、ＢｕＯＨ ２４質量部及びＴＢＰＥＨ ４．８質量部を含有する混合物を、前記反応容器中へ４時間で滴下し、滴下終了後、更に同温度で２０時間反応させて加水分解性シリル基を有する数平均分子量が１０，２００のビニル重合体（Ｒａ２−２）の有機溶剤溶液を得た。
次いで、Ａ−３ ０．０３質量部と脱イオン水 ７０質量部との混合物を、５分間で滴下し、更に同温度で１０時間攪拌して加水分解縮合反応させることで、ビニル重合体（Ｒａ２−２）の有する加水分解性シリル基と、前記ＰＴＭＳ及びＤＭＤＭＳ由来のポリシロキサンの有する加水分解性シリル基及びシラノール基とが結合した複合樹脂を含有する液を得た。
次いで、この液に合成例１で得られたＭＴＭＳの縮合物（ａ１’−１）２９８質量部、脱イオン水 ５０質量部を添加し、同温度で１０時間攪拌して加水分解縮合反応させたものを、合成例１と同様の条件で蒸留することによって生成したメタノール及び水を除去し、次いで、ＢｕＯＨ ２５０質量部を添加し、不揮発分が６０．０質量％の比較用樹脂組成物（Ｒ２）の溶液１，０００質量部を得た。 Comparative Example 2: Production of Comparative Resin Composition (R2)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 66 parts by mass of PTMS and 175 parts by mass of DMDS were charged, and the temperature was raised to 80 ° C.
Then, at the same temperature, a mixture containing 168 parts by mass of MMA, 31 parts by mass of BMA, 26 parts by mass of BA, 14 parts by mass of MPTS, 24 parts by mass of BuOH and 4.8 parts by mass of TBPEH is introduced into the reaction vessel for 4 hours It dripped and it made it react at the same temperature for 20 hours after completion | finish of dripping, and obtained the organic solvent solution of the vinyl polymer (Ra2-2) of the number average molecular weight 10,200 which has a hydrolysable silyl group.
Then, a mixture of 0.03 parts by mass of A-3 and 70 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, thereby obtaining a vinyl polymer (Ra2). There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group possessed by (-2) and the hydrolyzable silyl group and silanol group possessed by the PTMS and the DMMS derived from polysiloxane are bonded.
Next, 298 parts by mass of the MTMS condensate (a1'-1) obtained in Synthesis Example 1 and 50 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction. The product was subjected to distillation under the same conditions as in Synthesis Example 1 to remove methanol and water generated, and then 250 parts by mass of BuOH was added, and a comparative resin composition (R2 having a nonvolatile content of 60.0% by mass) 1,000 parts by weight of the solution of

（比較例３：比較用樹脂組成物（Ｒ３）の製造）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、ＢｕＯＨ １５０質量部、ＰＴＭＳ １１１質量部、ＤＭＤＭＳ ２９２質量部を仕込んで８０℃まで昇温した。
次いで、同温度でＡ−３ ０．０５質量部と脱イオン水 １１８質量部との混合物を、５分間で滴下し、更に同温度で１０時間攪拌して加水分解縮合反応させることで、前記ＰＴＭＳ及びＤＭＤＭＳ由来のポリシロキサンを含有する液を得た。
次いで、この液に合成例１で得られたＭＴＭＳの縮合物（ａ１’−１）４９７質量部、脱イオン水 ８４質量部を添加し、同温度で１０時間攪拌して加水分解縮合反応させたものを、合成例１と同様の条件で蒸留することによって生成したメタノール及び水を除去し、次いで、ＢｕＯＨ ２５０質量部を添加し、不揮発分が６０．０質量％の比較用樹脂組成物（Ｒ３）の溶液１，０００質量部を得た。 Comparative Example 3: Production of Comparative Resin Composition (R3)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 111 parts by mass of PTMS, and 292 parts by mass of DMDS were charged, and the temperature was raised to 80 ° C.
Then, a mixture of 0.05 parts by mass of A-3 and 118 parts by mass of deionized water is added dropwise over 5 minutes at the same temperature, and the PTMS is further subjected to a hydrolysis condensation reaction by stirring for 10 hours at the same temperature. And the liquid containing the polysiloxane derived from DMDMS was obtained.
Next, 497 parts by mass of the MTMS condensate (a1'-1) obtained in Synthesis Example 1 and 84 parts by mass of deionized water were added to this solution, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction. The product was subjected to distillation under the same conditions as in Synthesis Example 1 to remove methanol and water generated, and then 250 parts by mass of BuOH was added, and a comparative resin composition (R3 having a nonvolatile content of 60.0% by mass) 1,000 parts by weight of the solution of

（比較例４：比較用樹脂組成物（Ｒ４）の製造）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、ＢｕＯＨ １５０質量部、ＰＴＭＳ ４１質量部、ＤＭＤＭＳ ２６３質量部を仕込んで８０℃まで昇温した。
次いで、同温度でＭＭＡ ４２質量部、ＢＭＡ ８質量部、ＢＡ ７質量部、ＭＰＴＳ ４質量部、ＢｕＯＨ ６質量部及びＴＢＰＥＨ １．２質量部を含有する混合物を、前記反応容器中へ５時間で滴下し、滴下終了後、更に同温度で２０時間反応させて加水分解性シリル基を有する数平均分子量が１０，４００のビニル重合体（Ｒａ２−４）の有機溶剤溶液を得た。
次いで、Ａ−３ ０．０４質量部と脱イオン水 ９０質量部との混合物を、５分間で滴下し、更に同温度で１０時間攪拌して加水分解縮合反応させることで、ビニル重合体（Ｒａ２−４）の有する加水分解性シリル基と、前記ＰＴＭＳ及びＤＭＤＭＳ由来のポリシロキサンの有する加水分解性シリル基及びシラノール基とが結合した複合樹脂を含有する液を得た。
次いで、この液に合成例１で得られたＭＴＭＳの縮合物（ａ１’−１）５０１質量部、脱イオン水 ８５質量部を添加し、同温度で１０時間攪拌して加水分解縮合反応させたものを、合成例１と同様の条件で蒸留することによって生成したメタノール及び水を除去し、次いで、ＢｕＯＨ ２５０質量部を添加し、不揮発分が６０．０質量％の比較用樹脂組成物（Ｒ４）の溶液１，０００質量部を得た。 Comparative Example 4: Production of Comparative Resin Composition (R4)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 41 parts by mass of PTMS and 263 parts by mass of DMDMS were charged and the temperature was raised to 80 ° C.
Then, a mixture containing 42 parts by mass of MMA, 8 parts by mass of BMA, 7 parts by mass of BA, 4 parts by mass of MPTS, 6 parts by mass of BuOH and 1.2 parts by mass of TBPEH at the same temperature for 5 hours into the reaction vessel It dripped and after completion | finish of dripping, it was made to react at the same temperature for 20 hours, and the organic solvent solution of the vinyl polymer (Ra2-4) of the number average molecular weight 10,400 which has a hydrolysable silyl group was obtained.
Next, a mixture of 0.04 parts by mass of A-3 and 90 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, thereby obtaining a vinyl polymer (Ra2). There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group possessed by (4) and the hydrolyzable silyl group possessed by the PTMS and the polysiloxane derived from DMDMS and the silanol group are bonded.
Next, to this solution was added 501 parts by mass of the MTMS condensate (a1'-1) obtained in Synthesis Example 1 and 85 parts by mass of deionized water, and the mixture was stirred at the same temperature for 10 hours to cause a hydrolysis condensation reaction. The product was subjected to distillation under the same conditions as in Synthesis Example 1 to remove methanol and water formed, and then 250 parts by mass of BuOH was added, and a comparative resin composition (R4 having a nonvolatile content of 60.0% by mass) 1,000 parts by weight of the solution of

（比較例５：比較用樹脂組成物（Ｒ５）の製造）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、ＢｕＯＨ １５０質量部、ＰＴＭＳ ３３２質量部、ＤＭＤＭＳ ３５０質量部を仕込んで８０℃まで昇温した。
次いで、同温度でＭＭＡ ４２質量部、ＢＭＡ ８質量部、ＢＡ ７質量部、ＭＰＴＳ ４質量部、ＢｕＯＨ ６質量部及びＴＢＰＥＨ １．２質量部を含有する混合物を、前記反応容器中へ６時間で滴下し、滴下終了後、更に同温度で２０時間反応させて加水分解性シリル基を有する数平均分子量が１０，０００のビニル重合体（Ｒａ２−５）の有機溶剤溶液を得た。
次いで、Ａ−３ ０．０７質量部と脱イオン水 １９５質量部との混合物を、５分間で滴下し、更に同温度で１０時間攪拌して加水分解縮合反応させることで、ビニル重合体（Ｒａ２−５）の有する加水分解性シリル基と、前記ＰＴＭＳ及びＤＭＤＭＳ由来のポリシロキサンの有する加水分解性シリル基及びシラノール基とが結合した複合樹脂を含有する液を得た。
次いで、この液に３−グリシドキシプロピルトリメトキシシラン １５３質量部、脱イオン水 ３５質量部を添加し、同温度で１０時間攪拌して加水分解縮合反応させたものを、合成例１と同様の条件で蒸留することによって生成したメタノール及び水を除去し、次いで、ＢｕＯＨ ２５０質量部を添加し、不揮発分が６０．０質量％の比較用樹脂組成物（Ｒ５）の溶液１，０００質量部を得た。 Comparative Example 5 Production of Comparative Resin Composition (R5)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 150 parts by mass of BuOH, 332 parts by mass of PTMS and 350 parts by mass of DMDMS were charged and the temperature was raised to 80 ° C.
Then, a mixture containing 42 parts by mass of MMA, 8 parts by mass of BMA, 7 parts by mass of BA, 4 parts by mass of MPTS, 6 parts by mass of BuOH and 1.2 parts by mass of TBPEH at the same temperature for 6 hours into the reaction vessel It dripped and it made it react at the same temperature for 20 hours after completion | finish of dripping, and obtained the organic solvent solution of the vinyl polymer (Ra2-5) of the number average molecular weight 10,000 which has a hydrolysable silyl group.
Next, a mixture of 0.07 parts by mass of A-3 and 195 parts by mass of deionized water is added dropwise over 5 minutes, and the mixture is further stirred for 10 hours at the same temperature to cause a hydrolysis condensation reaction, thereby obtaining a vinyl polymer (Ra2). There was obtained a liquid containing a composite resin in which the hydrolyzable silyl group possessed by (-5) and the hydrolyzable silyl group and silanol group possessed by the PTMS and the polysiloxane derived from DMDS are bonded.
Subsequently, 153 parts by mass of 3-glycidoxypropyltrimethoxysilane and 35 parts by mass of deionized water were added to this solution, and the mixture was stirred for 10 hours at the same temperature for hydrolysis and condensation reaction, as in Synthesis Example 1. Of methanol and water generated by distillation under the following conditions, and then adding 250 parts by mass of BuOH, and 1,000 parts by mass of a solution of a comparative resin composition (R5) having a nonvolatile content of 60.0% by mass. I got

（比較例６：比較用樹脂組成物（Ｒ６）の製造）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、ＢｕＯＨ ６９０質量部を仕込んで８０℃まで昇温した。
次いで、同温度でＭＭＡ １９３質量部、ＢＭＡ ３６質量部、ＢＡ ３０質量部、ＭＰＴＳ １７質量部、ＢｕＯＨ ２８質量部及びＴＢＰＥＨ ５．５質量部を含有する混合物を、前記反応容器中へ３時間で滴下し、滴下終了後、更に同温度で２０時間反応させて数平均分子量が１０，３００のビニル重合体（Ｒａ２−６）の有機溶剤溶液を得た。
次いで、比較例３で得た比較用樹脂組成物（Ｒ３）８０８質量部と不揮発分が２８．０質量％のビニル重合体（Ｒａ２−６）の有機溶剤溶液 １９２質量部とを混合し、同温度で１時間攪拌することで不揮発分が５３．８質量％の比較用樹脂組成物（Ｒ６）の溶液１，０００質量部を得た。 Comparative Example 6: Production of Comparative Resin Composition (R6)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 690 parts by mass of BuOH were charged and the temperature was raised to 80 ° C.
Then, a mixture containing 193 parts by mass of MMA, 36 parts by mass of BMA, 30 parts by mass of BA, 17 parts by mass of MPTS, 28 parts by mass of BuOH and 5.5 parts by mass of TBPEH at the same temperature for 3 hours into the reaction vessel It dripped and made it react at the same temperature for 20 hours after completion | finish of dripping, and the organic solvent solution of the vinyl polymer (Ra2-6) of a number average molecular weight 10,300 was obtained.
Subsequently, 808 parts by mass of the resin composition for comparison (R3) obtained in Comparative Example 3 and 192 parts by mass of an organic solvent solution of a vinyl polymer (Ra2-6) having a nonvolatile content of 28.0% by mass are mixed, The solution was stirred at a temperature for 1 hour to obtain 1,000 parts by weight of a solution of a comparative resin composition (R6) having a non-volatile content of 53.8% by mass.

［保存安定性の評価］
上記で得られた耐汚染性付与剤及び比較用樹脂組成物の保存安定性を、５０℃において、３０日間保存したものの粘度（いわゆる経時粘度）を分子とし、初期粘度を分母とする粘度比で評価した。粘度測定は、Ｅ型粘度計（東京計器株式会社製）を用いて２５℃にて行った。また、サンプルの保存は、得られた硬化性樹脂組成物をガラス製チュ−ブに入れて、５０℃の環境下で３０日間静置せしめることによって行った。この粘度比が１に近い値であるほど、保存安定性が優れているということを意味しており、粘度比が０．９以上１．１以下で保存安定性が非常に優れている樹脂であるものと判定した。 [Evaluation of storage stability]
The storage stability of the stain resistance imparting agent and the resin composition for comparison obtained above is the viscosity ratio of the viscosity after storage for 30 days at 50 ° C. (so-called viscosity over time) as the numerator and the initial viscosity as the denominator evaluated. The viscosity was measured at 25 ° C. using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). Moreover, the storage of the sample was performed by putting the obtained curable resin composition in a glass tube and allowing it to stand for 30 days under an environment of 50 ° C. As the viscosity ratio is closer to 1, it means that the storage stability is more excellent, and it is a resin with a viscosity ratio of 0.9 or more and 1.1 or less and very excellent in storage stability. It was determined that there was something.

上記の実施例１〜９及び比較例１〜６の評価結果を表１〜３に示す。   The evaluation results of Examples 1 to 9 and Comparative Examples 1 to 6 described above are shown in Tables 1 to 3.

Figure 2019112488
Figure 2019112488

Figure 2019112488
Figure 2019112488

Figure 2019112488
Figure 2019112488

（実施例１０：コーティング剤（１）の調製）
水性樹脂（１）（ＤＩＣ株式会社製「バーノックＷＤ−５５１」、アクリル系水性樹脂）１００質量部、硬化剤（１）（ＤＩＣ株式会社製「バーノックＤＮＷ−５５００」、ポリイソシアネート硬化剤）３０質量部及び耐汚染性付与剤（１）０．５質量部を混合し、コーティング剤（１）を得た。 Example 10 Preparation of Coating Agent (1)
100 parts by mass of aqueous resin (1) ("Barnock WD-551" manufactured by DIC Corporation, acrylic aqueous resin), 30 parts by weight of curing agent (1) ("Barnock DNW-5500" manufactured by DIC Corporation, polyisocyanate curing agent) Parts and 0.5 parts by mass of the stain resistance imparting agent (1) were mixed to obtain a coating agent (1).

（実施例１１〜２４：コーティング剤（２）〜（１５）の調製）
下記表４〜６に示す配合に変更した以外は実施例１０と同様に操作することにより、コーティング剤（２）〜（１５）を得た。 Examples 11 to 24: Preparation of Coatings (2) to (15)
Coating agents (2) to (15) were obtained by operating in the same manner as in Example 10 except for changing to the formulations shown in Tables 4 to 6 below.

（比較例７〜１５：コーティング剤（Ｒ１）〜（Ｒ９）の調製）
下記表７及び８に示す配合に変更した以外は実施例１０と同様に操作することにより、コーティング剤（Ｒ１）〜（Ｒ９）を得た。 (Comparative Examples 7 to 15: Preparation of Coating Agents (R1) to (R9))
Coating agents (R1) to (R9) were obtained by operating in the same manner as in Example 10 except for changing to the formulations shown in Tables 7 and 8 below.

［評価用硬化塗膜の作製］
上記で得られたコーティング剤を、株式会社エンジニアリングテストサービス製のクロメート処理されたアルミ板上にアクリルポリオール・ポリイソシアネート白色塗料が塗装された塗装板を水研ぎして得られた白色塗板上に、硬化塗膜の膜厚が３０μｍとなるように塗装し、２３℃の環境下で１週間乾燥させて評価用クリア硬化塗膜を得た。 [Preparation of cured film for evaluation]
On the white coated board obtained by water-grinding the coated board in which the acrylic polyol polyisocyanate white paint was coated on the chromate-treated aluminum board manufactured by Engineering Test Service Co., Ltd. The coating was applied so that the thickness of the cured coating was 30 μm, and was dried for 1 week in an environment of 23 ° C. to obtain a clear cured coating for evaluation.

［塗膜外観の評価］
上記で得られた硬化塗膜の初期状態目視で観察し、下記の基準で塗膜外観を評価した。
○：ブツ等の異物や白化の発生が認められない。
△：若干のブツ等の異物や白化の発生が認められる。
×：著しいブツ等の異物や白化の発生が認められる。 [Evaluation of coating film appearance]
The initial state of the cured coating film obtained above was observed visually, and the coating film appearance was evaluated based on the following criteria.
○: No occurrence of foreign substances such as bumps or whitening is observed.
Fair: Occurrence of some foreign substances such as bumps and whitening are observed.
X: Significant occurrence of extraneous substances such as lumps and whitening are observed.

［耐汚染性の評価」
上記で得られた硬化塗膜を、大阪府高石市のＤＩＣ株式会社堺工場内において１ヶ月間、３ヶ月間、６ヶ月間の曝露試験を行った。
ここで、曝露試験後の未洗浄の試験塗膜と、曝露試験前の試験塗膜との色差（ΔＥ）を、コニカミノルタセンシング株式会社製の「ＣＭ−３５００ｄ」を用いて評価した。前記色差（ΔＥ）が小さいほど、耐汚染性が良好であることを示す。 [Evaluation of contamination resistance]
The cured coating film obtained above was subjected to an exposure test for 1 month, 3 months and 6 months in the DIC Corporation Sakai plant in Takaishi City, Osaka Prefecture.
Here, the color difference (ΔE) between the unwashed test coating after the exposure test and the test coating before the exposure test was evaluated using “CM-3500 d” manufactured by Konica Minolta Sensing, Inc. The smaller the color difference (ΔE), the better the stain resistance.

上記の実施例１０〜２４及び比較例７〜１５の評価結果を表４〜８に示す。   The evaluation results of Examples 10 to 24 and Comparative Examples 7 to 15 described above are shown in Tables 4 to 8.

Figure 2019112488
Figure 2019112488

Figure 2019112488
Figure 2019112488

Figure 2019112488
Figure 2019112488

Figure 2019112488
Figure 2019112488

Figure 2019112488
Figure 2019112488

上記の表４〜８中の略号は、下記のものである。
水性樹脂（１）：ＤＩＣ株式会社製「バーノックＷＤ−５５１」、アクリル系水性樹脂
水性樹脂（２）：ＤＩＣ株式会社製「セラネートＷＳＡ−１０７０」、ポリシロキサンアクリル複合系水性樹脂
水性樹脂（３）：ＤＩＣ株式会社製「ハイドランＷＬＳ−２１０」、ウレタン系水性樹脂
硬化剤（１）：ＤＩＣ株式会社製「バーノックＤＮＷ−５５００」、水分散性ポリイソシアネート硬化剤
硬化剤（２）：ＤＩＣ株式会社製「ウォーターゾールＷＳＡ−９５０」、加水分解性シリル基含有硬化剤 The abbreviations in the above Tables 4 to 8 are as follows.
Aqueous resin (1): "Barnock WD-551" manufactured by DIC Corporation, acrylic aqueous resin aqueous resin (2): "Ceranate WSA-1070" manufactured by DIC Corporation, polysiloxane acrylic composite aqueous resin aqueous resin (3) : "Hydran WLS-210" manufactured by DIC Corporation, urethane based aqueous resin curing agent (1): "Barnock DNW-5500" manufactured by DIC Corporation, water dispersible polyisocyanate curing agent curing agent (2): manufactured by DIC Corporation "Watersol WSA-950", hydrolyzable silyl group containing curing agent

実施例１〜９の本発明の耐汚染性付与剤は保存安定性に優れ、これらを水性樹脂に添加して得られる塗膜は塗膜外観に優れ、耐汚染性に優れることが確認された。   The stain resistance imparting agent of the present invention of Examples 1 to 9 is excellent in storage stability, and a coating film obtained by adding these to an aqueous resin is excellent in coating film appearance, and excellent in staining resistance was confirmed. .

比較例１、２、７及び８は、複合樹脂（Ａ）中のポリシロキサン（ａ１）が、本発明の下限である７５質量％より低い例であるが、得られる塗膜の耐汚染性が不十分であることが確認された。   Comparative Examples 1, 2, 7 and 8 are examples in which the polysiloxane (a1) in the composite resin (A) is lower than the lower limit of 75% by mass of the present invention, but the stain resistance of the resulting coating film is It was confirmed to be insufficient.

比較例３及び９は、重合体（ａ２）を含有しない例であるが、得られる塗膜の外観に異常がみられ、また、耐汚染性が不十分であることが確認された。   Comparative Examples 3 and 9 are examples in which the polymer (a2) is not contained, but the appearance of the obtained coating film is abnormal, and it is also confirmed that the stain resistance is insufficient.

比較例４及び１０は、ポリシロキサン（ａ１）中の構造単位（Ｕ１）が、本発明の下限である１０質量％より少ない例であるが、保存安定性が不十分であり、得られる塗膜の耐汚染性が不十分であることが確認された。   Comparative Examples 4 and 10 are examples in which the structural unit (U1) in the polysiloxane (a1) is less than 10% by mass, which is the lower limit of the present invention, but the storage stability is insufficient and the obtained coating film is obtained It was confirmed that the stain resistance of the

比較例５及び１１は、ポリシロキサン（ａ１）中に構造単位（Ｕ２）を有しない例であるが、得られる塗膜の耐汚染性が不十分であることが確認された。   Although comparative examples 5 and 11 are examples which do not have a structural unit (U2) in polysiloxane (a1), it was confirmed that the stain resistance of the obtained coating film is inadequate.

比較例６及び１２は、ポリシロキサン溶液とビニル系重合体溶液をブレンドした例であるが、保存安定性が不十分であり、得られる塗膜の外観に異常がみられ、また、耐汚染性が不十分であることが確認された。   Comparative Examples 6 and 12 are examples in which a polysiloxane solution and a vinyl polymer solution are blended, but the storage stability is insufficient, the appearance of the obtained coating film is abnormal, and the stain resistance is also obtained. Was confirmed to be inadequate.

比較例１３〜１５は、本発明の耐汚染性付与剤を含有しない例であるが、得られる塗膜の耐汚染性が不十分であることが確認された。   Although Comparative Examples 13-15 are the examples which do not contain the stain resistance imparting agent of this invention, it was confirmed that the stain resistance of the obtained coating film is inadequate.

Claims (5)

一般式（１）又は（２）で表される構造単位（Ｕ１）、及び一般式（３）で表される構造単位（Ｕ２）を有するポリシロキサン（ａ１）と重合体（ａ２）とが一般式（４）で表される結合により結合した複合樹脂（Ａ）が、媒体中に溶解又は分散している耐汚染性付与剤であって、前記複合樹脂（Ａ）中の前記ポリシロキサン（ａ１）が７５〜９９質量％であり、前記ポリシロキサン（ａ１）中の前記構造単位（Ｕ１）が１０〜５５質量％であることを特徴とする耐汚染性付与剤。
Figure 2019112488
Figure 2019112488
 （一般式（１）、（２）中のＲ１は芳香族炭化水素置換基を表し、Ｒ２は芳香族炭化水素置換基又はアルキル基を表す。）
Figure 2019112488
 （一般式（３）中のＲ３はメチル基又はエチル基を表す。）
Figure 2019112488
 The polysiloxane (a1) having the structural unit (U1) represented by the general formula (1) or (2) and the structural unit (U2) represented by the general formula (3) and the polymer (a2) are generally The composite resin (A) bonded by the bond represented by the formula (4) is a stain resistance imparting agent dissolved or dispersed in a medium, and the polysiloxane (a1) in the composite resin (A) And the structural unit (U1) in the polysiloxane (a1) is 10 to 55% by mass.
Figure 2019112488
Figure 2019112488
 (R 1 in the general formulas (1) and (2) represents an aromatic hydrocarbon substituent, and R 2 represents an aromatic hydrocarbon substituent or an alkyl group.)
Figure 2019112488
 (R 3 in general formula (3) represents a methyl group or an ethyl group.)
Figure 2019112488
 前記構造単位（Ｕ１）が、フェニルトリメトキシシランまたはジフェニルジメトキシシラン由来の構造単位である請求項１記載の耐汚染性付与剤。   The stain resistance imparting agent according to claim 1, wherein the structural unit (U1) is a structural unit derived from phenyltrimethoxysilane or diphenyldimethoxysilane. 請求項１又は２記載の耐汚染性付与剤を含有することを特徴とするコーティング剤。   A coating agent comprising the stain resistance imparting agent according to claim 1 or 2. 水性樹脂を含有する請求項３記載のコーティング剤。   The coating agent according to claim 3 containing an aqueous resin. 請求項３又は４記載のコーティング剤の塗膜を有することを特徴とする物品。   An article having a coating of the coating agent according to claim 3 or 4.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023055176A (en) * 2021-10-05 2023-04-17 Ｄｉｃグラフィックス株式会社 Antibacterial and antiviral agents, coating agents and substrates

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1036515A (en) * 1996-07-30 1998-02-10 Dainippon Ink & Chem Inc Aqueous resin, method for producing the same, and aqueous curable resin composition containing the same
JPH11279408A (en) * 1997-06-02 1999-10-12 Dainippon Ink & Chem Inc Water-based resin production method, water-based curable resin composition and water-based paint
JP2006052310A (en) * 2004-08-11 2006-02-23 Kansai Paint Co Ltd Method for producing polysiloxane composite polymer particle
JP2008038116A (en) * 2006-08-10 2008-02-21 Asahi Kasei Chemicals Corp High durability emulsion
JP2016000808A (en) * 2014-05-21 2016-01-07 旭化成ケミカルズ株式会社 Water-based coating agent composition, coating film, and painted product

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1036515A (en) * 1996-07-30 1998-02-10 Dainippon Ink & Chem Inc Aqueous resin, method for producing the same, and aqueous curable resin composition containing the same
JPH11279408A (en) * 1997-06-02 1999-10-12 Dainippon Ink & Chem Inc Water-based resin production method, water-based curable resin composition and water-based paint
JP2006052310A (en) * 2004-08-11 2006-02-23 Kansai Paint Co Ltd Method for producing polysiloxane composite polymer particle
JP2008038116A (en) * 2006-08-10 2008-02-21 Asahi Kasei Chemicals Corp High durability emulsion
JP2016000808A (en) * 2014-05-21 2016-01-07 旭化成ケミカルズ株式会社 Water-based coating agent composition, coating film, and painted product

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023055176A (en) * 2021-10-05 2023-04-17 Ｄｉｃグラフィックス株式会社 Antibacterial and antiviral agents, coating agents and substrates

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