JPH04100845A - resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a resin composition, and more specifically, it has excellent non-stick properties, lubricity, anti-blocking properties, as well as migration resistance and bleed resistance. The purpose of the present invention is to provide a vinyl chloride resin composition.

(Prior Art) Silicon compounds, especially siloxane (silicone) oil, have traditionally been used as antifoaming agents, mold release agents, and fibers due to their excellent properties such as non-adhesiveness, lubricity, water repellency, flexibility, and heat resistance. It is widely used for processing agents, various coating agents, paints, inks, and electrical/electronic parts.

In addition, by incorporating a siloxane compound into the vinyl chloride resin, the vinyl chloride resin has non-adhesive properties, lubricity,
Attempts have been made to provide functions such as blocking resistance and stain resistance.

(The problem that the invention is trying to solve) However,
When a conventional siloxane compound is incorporated into a vinyl chloride resin, although it is sometimes satisfactory in terms of non-stick properties, lubricity, anti-blocking properties, etc., the siloxane compound used is essentially compatible with the vinyl chloride resin. Due to its low solubility, the siloxane compound bleeds out over time on the surface of the molded product made of the resin composition, causing various problems.

As a method to solve such problems, a method has been considered to use a siloxane compound with a reactive functional group and cure it in a resin composition to eliminate bleed-out. The siloxane compound having a functional group contains a considerable amount of a non-reactive siloxane compound having no active hydrogen group as an impurity, and the problem of bleed-out cannot be satisfactorily solved.

Of course, it is theoretically possible to purify siloxane compounds that have reactive functional groups, but since the physical properties of non-reactive compounds are almost the same as those of reactive compounds, it is difficult to separate these non-reactive compounds. is very difficult and not industrially possible.

Therefore, the object of the present invention is to provide non-adhesive and lubricious properties.

The object of the present invention is to provide a siloxane-modified vinyl chloride resin composition that has excellent migration resistance, bleeding resistance, etc. in addition to blocking resistance.

(Means for solving problems) The above objects are achieved by the present invention as described below.

That is, the present invention is characterized in that it is made by copolymerizing a siloxane compound having an active hydrogen group and a lactone compound, and is made of a siloxane-modified polyester resin and a vinyl chloride resin that do not substantially contain unreacted siloxane compounds. This is a resin composition.

(For use in I) By copolymerizing a siloxane compound having an active hydrogen group with a lactone and treating it under reduced pressure after the reaction, the siloxane compound having an active hydrogen group has become a copolymer with a lactone compound, so it can be treated under reduced pressure. On the other hand, non-reactive siloxane compounds are removed under reduced pressure because they do not have a high molecular weight.

By doing this, the non-reactive siloxane compound contained in the siloxane compound used as a raw material can be easily removed, and by mixing the siloxane-modified polyester resin with the vinyl chloride resin, non-adhesive, A vinyl chloride resin composition having excellent migration resistance, bleed resistance, etc. in addition to lubricity and blocking resistance is provided.

(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments.

The siloxane-modified polyester resin used in the present invention is obtained by copolymerizing a siloxane compound having an active hydrogen group and a lactone compound, and then subjecting the copolymerization to a reduced pressure treatment.

Preferred examples of the active hydrogen group-containing siloxane compound used in the present invention include the following compounds.

(1) Amino-modified siloxane oil (m: 0-200) (n=2-10) (m; 1-10, n=2-10, R"CH3 or 0CH
3) (Branch point = 2-3, R = lower alkyl group, 1; 2-
200.0=2~200, n:2~200) (m=1~
10, n: 2-10, R=CH, or OCH,, R'=
aliphatic divalent group or aliphatic ether group) (n=1-200, R=lower alkyl group) Epoxy-modified siloxane oil CH3 CH3 (n=1-200) (m=1-101 n=2-10 ) CH3 CH3 The above epoxy compound can be used by reacting with polyol, polyamine, polycarboxylic acid, etc. so that it has an active hydrogen group at the end.

(m=1~10, n=2-10) Alcohol-modified siloxane oil CH1CH3 CH3 CH.

CH3 CH.

HOC3H, SiO(Sin), SiC, HaOHC
H3CH3CH.

(n: 1-200) (n=1-200) CH3 CH.

(Branch point・2-3, R・lower alkyl group, (m=1-10, n=2-1O1 R=aliphatic divalent group or 1: 2-200, m=2-200, n= 2-200) Aliphatic ether group) (CHl)isio(SiO), 5ifCH3)iCH
.

CH.

CH.

(n; 1-10) (n=0-200) 50, n=2-5) CH3 Mercapto-modified siloxane oil HO (02H40) 1 (S10) ffi (C2H40)
l, HCH3CH.

CH.

CH3 CH3 CH,SiO(Sin) , 1(Sin) nSi
(CH312 (1=1-101 m; 10-200, n=1-5) CH3CH3 C,H,SH (m:1-1O1 n=2-10) C,H,5H CH3CH3 CH.

(CH3), 5iO(SiO). 5i(CH3)-(n
=1~200, R・lower alkyl) CH3 (n:2~10) 0 [Si (CH3) 2o] 5i(CH3)3 H20H (R・lower alkyl group, ・Hydrogen atom, Al (branch point・2~ 3, R; lower alkyl group, kyl group, K=1-250, l:0-5, m=0-1=2-20
0, m=2~200. 2-200) 50, n=1-5) H (n; 1-200, R, lower alkyl group) (R=lower alkyl group, R.

= hydrogen atom, alkyl group, k = 1-250, l = 0-5, m = o ~ (5) carboxyl-modified siloxane oil (m = 1-1O1n: 2-
10) (n: 1-200) (branch point = 2-3, R: lower alkyl group, 1 = 2-20
0, m=2-200, n; 2-200) (n=1-20
0, R: lower alkyl group) The siloxane compounds having active hydrogen groups as described above are preferred examples of siloxane compounds in the present invention, and the present invention is not limited to these examples. The compound and other siloxane compounds are currently commercially available and can be easily obtained from the market, and any of them can be used in the present invention.

In the present invention, the lactone compound reacted with the siloxane compound having an active hydrogen group is a lactone compound that can form a polyester by conventional lactone ring-opening polymerization, such as ε-caprolactone, δ-valerolactone, etc. Alkyl, halogen, haloalkyl,
Mono- or di-substituted derivatives of alkoxy, alkoxyalkyl, etc. can be used as well. Particularly suitable lactone compounds are ε-caprolactone and derivatives thereof.

The reaction between the siloxane compound and the lactone compound is carried out by mixing the two and reacting them at a temperature of 150 to 200° C. for several hours to more than ten hours, preferably using a suitable catalyst under a nitrogen stream. A desired siloxane-modified polyester copolymer is obtained.

Although both can be reacted at any reaction ratio, for the purpose of the present invention, it is preferable to react at a ratio such that the siloxane segment occupies 5 to 80% by weight in the resulting copolymer. If the amount of siloxane compound used is too small, the resulting resin composition will have non-stick properties,
Blocking resistance and the like will be insufficient, while too much of it will reduce the film-forming properties and film strength of the resulting resin composition, which is not preferable.

The copolymer obtained as described above contains the non-reactive siloxane compound contained in the siloxane compound used, and although it varies depending on the siloxane compound used and the copolymerization ratio, usually Approximately 1.0 of the copolymer
It is contained as an impurity in a proportion of ~5% by weight.

Although the above impurities are difficult to separate at the raw material stage, in the present invention, the copolymerization is performed at a temperature of about 100 to 250°C, preferably under an inert atmosphere such as nitrogen gas, at a pressure of 10 mmHg, preferably after the copolymerization. can be easily removed by vacuum treatment under conditions of 5 mmHg or less.

A polyester resin containing substantially no unreacted siloxane compound is obtained. In the present invention, the term "substantially free" refers to one in which the content of unreacted siloxane compounds is less than 10%.

The above-mentioned polyester resin may have any molecular weight, but in consideration of usability, it preferably has a molecular weight of about 1,000 to 30,000, and the molecular weight can be adjusted by using known techniques as is.

In addition, the copolymer has reactive hydroxyl groups at the ends, and these end groups may be left as they are, but they may be blocked with a blocking agent such as acetic anhydride, or treated with various crosslinking agents. It is possible to crosslink (cure) it with (curing agent).

The vinyl chloride resin used in the present invention is a homopolymer of vinyl chloride, a homopolymer of vinylidene chloride, a copolymer or a tertiary copolymer of vinyl chloride or vinylidene chloride, and various other copolymerizable monomers. Including polymers. Examples of copolymerizable monomers include vinyl esters, vinyl ethers, vinylidene chloride, lower olefins, vinyl acetate, vinyl bromide, vinyl fluoride, aromatic vinyl compounds such as styrene, heterocyclic vinyl compounds such as vinylpyridine, and acrylics. Examples include acids and derivatives thereof, conjugated diene compounds such as butadiene, and the like.

Further, the above vinyl chloride resin may be a blend with other polymers such as styrene acrylonitrile copolymer and styrene-methyl methacrylate copolymer.

The blending ratio of the siloxane-modified polyester resin and the vinyl chloride resin is not particularly limited and varies depending on the purpose of use, but the weight ratio of the former to the latter is 200:10 to 1.
0:200, preferably 200:100-100:20
The range is 0.

The mixing of the two may be done by simply mixing the powders together, but it is preferable to melt and knead them using a mixing roll, an extruder, etc. to homogenize them.

The resin composition may also contain other usual additives such as stabilizers such as fatty acid metal soaps, colorants, plasticizers, antistatic agents, ultraviolet absorbers, and blowing agents.

The resin composition of the present invention as described above is very useful as various molding materials, materials for synthetic leather, fiber coating agents, surface treatment agents, forming release layers of release papers, etc., and as binders for paints, printing inks, etc. .

(Example) Next, the present invention will be described in more detail by giving examples, comparative examples, and evaluation examples. In the text, parts or percentages are based on weight unless otherwise specified.

Example 1 H2 (m and n are values that give an amine equivalent of 3,800) 240 parts of ε-caprolactone and the above structure were placed in a reactor equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, and a reflux condenser. (
1) and 0.05 part of tetrabutyl titanate were charged, and this mixture was reacted for 10 hours at a temperature of 180"C under a nitrogen stream. As the reaction progressed, the reaction occurred. The viscosity of the substance increases.

Thereafter, the reaction was continued for 1 hour at 180° C. under a reduced pressure of 5 mmHg to complete the reaction and completely remove the non-reactive siloxane compound and unreacted substances contained in the raw material siloxane compound. The amount of unreacted siloxane compound removed was 12 parts.

Thereafter, 15 parts of acetic anhydride was added at 140°C, and 15 parts of acetic anhydride was added under reflux.
The hydroxyl groups in the product are completely acetylated by reacting for a long time,
At the same temperature, add by-product acetic acid and unreacted acetic anhydride to 5 mmH.
It was removed under reduced pressure at g.

The resulting product is a spiral polysiloxane with a melting point of 78°C.
It is a polyester copolymer.

Next, 80 parts of the above product, 100 parts of vinyl chloride resin with a degree of polymerization of 1050, 1.3 parts of calcium stearate and 1.3 parts of zinc stearate were mixed on a heated roll at 165°C.
The mixture was kneaded for 2 minutes to obtain a sheet-like resin composition of the present invention.

This mixed wire sheet was further placed in a heat breather at 175℃ for 200℃.
Heat pressed at a pressure of Kg/crrr for 5 minutes to a thickness of approximately 1m.
A test sheet of m was obtained.

Example 2 CH3CH3CH3CH3 CH3-SiO(SiO)II(SiO),, 5i-C
H3(2)CH3CH3(CH2)3CH3 NHC284NH2 (m and n are values that give an amine equivalent of 3,500) In the same manner as in Example 1, 160 parts of ε-caprolactone,
140 parts of amino-modified siloxane oil having the above structure (2) and 0.04 part of tetrabutyl titanate were charged and reacted at a temperature of 180° C. for 10 hours under a nitrogen stream. As the reaction progresses, the viscosity of the reactant increases.

Thereafter, the reaction was continued for 1 hour at 180° C. under a reduced pressure of 5 mmHg to complete the reaction and completely remove non-reactive siloxane compounds and unreacted substances contained in the raw material siloxane compound. The amount of unreacted siloxane compound removed was 15 parts.

Thereafter, 15 parts of acetic anhydride was added at 140°C, and 15 parts of acetic anhydride was added under reflux.
The hydroxyl groups in the product are completely acetylated by reacting for a long time,
At the same temperature, add by-product acetic acid and unreacted acetic anhydride to 5 mmH.
It was removed under reduced pressure at g.

The resulting product is a spiral polysiloxane with a melting point of 76°C.
It is a polyester copolymer.

Next, 80 parts of the above product, 100 parts of vinyl chloride resin with a degree of polymerization of 1050, 1.3 parts of calcium stearate and 1.3 parts of zinc stearate were mixed on a heated roll at 165°C.
The mixture was kneaded for 2 minutes to obtain a sheet-like resin composition of the present invention.

This kneaded sheet was further placed in a heat press at 175℃ for 200℃.
Heat pressed for 5 minutes at a pressure of Kg/ctd to a thickness of approximately 1mm.
A test sheet was obtained.

Example 3 H (m and n are values that give a hydroxyl value of 25) Example 1
In the same manner as above, 200 parts of ε-caprolactone and 1 alcohol-modified siloxane oil having the above structure (3) were added.
60 parts and 0.05 part of tetrabutyl titanate were charged, and the mixture was reacted at a temperature of 180° C. for 10 hours under a nitrogen stream. As the reaction progresses, the viscosity of the reactant increases.

Thereafter, the reaction was continued for 1 hour at 180° C. under a reduced pressure of 4 mmHg to complete the reaction and completely remove the non-reactive siloxane compound and unreacted substances contained in the raw material siloxane compound. The amount of unreacted siloxane compound removed was 12 parts.

Thereafter, 20 parts of acetic anhydride was added at 140°C, and 1
The hydroxyl groups in the product are completely acetylated by reacting for a long time,
At the same temperature, add by-product acetic acid and unreacted acetic anhydride to 5 mmH.
It was removed under reduced pressure at g.

The resulting product is a spiral polysiloxane with a melting point of 78°C.
It is a polyester copolymer.

Next, 80 parts of the above product, 100 parts of vinyl chloride resin with a degree of polymerization of 1050, 1.3 parts of calcium stearate and 1.3 parts of zinc stearate were mixed on a heated roll at 165°C.
The mixture was kneaded for 2 minutes to obtain a sheet-like resin composition of the present invention.

This mixed wire sheet was further placed in a heat press at 175℃ for 200℃.
Heat pressed for 5 minutes at a pressure of Kg/crr1' to a thickness of about 1
A test sheet of mm was obtained.

Example 4 (:, H40H (m and n are values that give a hydroxyl value of 32) Example 1
In the same manner as above, 180 parts of ε-caprolactone and 1 alcohol-modified siloxane oil having the above structure (4) were added.
60 parts and 0.04 part of tetrabutyl titanate were charged, and the mixture was reacted for 10 hours at a temperature of 180''C under a nitrogen stream.

As the reaction progresses, the viscosity of the reactant increases.

Thereafter, the reaction was continued for 1 hour at 180° C. under a reduced pressure of 3 mmHH to complete the reaction and completely remove non-reactive siloxane compounds and unreacted substances contained in the raw material siloxane compound. The amount of unreacted siloxane compound removed was 10 parts.

Thereafter, 16 parts of acetic anhydride was added at 140°C, and 16 parts of acetic anhydride was added under reflux.
The hydroxyl groups in the product are completely acetylated by reacting for a long time,
At the same temperature, add 5 m of by-product acetic acid and unreacted acetic anhydride.
Removed in vacuo at m Hg.

The resulting product is a spiral polysiloxane with a melting point of 75°C.
It is a polyester copolymer.

Next, 80 parts of the above product, 100 parts of hinyl chloride resin with a degree of polymerization of 1050, 1.3 parts of calcium stearate, and 1.3 parts of zinc stearate were mixed on a heated roll at 165°C.
The mixture was kneaded for 2 minutes to obtain a sheet-like resin composition of the present invention.

This kneaded sheet was further placed in a heat press at 175℃ for 200℃.
Heat pressed at a pressure of Kg/ctf for 5 minutes to a thickness of approximately 1mm.
A test sheet was obtained.

Comparative Examples 1 to 4 A resin composition was prepared with the following formulation, and a test sheet having a thickness of about 1 mm was obtained in the same manner as in the example.

80 parts Vinyl chloride resin (degree of polymerization 1050) 100 parts Calcium stearate 13 parts Zinc stearate
13 parts polyester plasticizer (average molecular weight 2000, manufactured by Dainichiseika Chemical Industry Co., Ltd. SO part vinyl chloride resin polymerization degree 1050) 100 parts calcium stearate 1.3 parts zinc stearate
Comparison of 13 parts ±1 DOP 72 parts Silicone oil 8 parts Vinyl chloride resin (degree of polymerization 10501 100 parts Calcium stearate
1.3 parts zinc stearate 1.
3 parts Technical comparison A Polyester plasticizer (average molecular weight 2000, manufactured by Dainichiseika Kogyo ■) 72 parts Silicone oil
8 parts vinyl chloride resin (degree of polymerization 10
50) 100 parts calcium stearate
1.3 parts Zinc stearate 1.3
Furthermore, if more than 8 parts of silicone oil was added to 100 parts of vinyl chloride resin, processing was difficult under the above processing conditions, and a homogeneous vinyl chloride resin sheet could not be obtained.

Evaluation Example Various physical properties of the test sheets of the above Examples and Comparative Examples were measured, and the results shown in Table 1 below were obtained.

Anti-blocking property: The test sheets were stacked and pressed together under a load of Ikg, and placed in an atmosphere of 45°C and 80% RH for 1 hour.
Stored for a week and measured the force required to peel off the sheet after storage (180° billing strength g/15 mm width) Extractability: Change over time based on Ministry of Health and Welfare Notification 178: Test sheet at 45° and 80% It was stored in an RH environment for one week, and after storage it was determined whether there was any bleeding on the surface.

○No nib word.

△Nibleed is observed.

X: Quite severe bleeding is observed.

(Effects) According to the present invention as described above, a vinyl chloride resin composition is provided which has excellent migration resistance, bleed resistance, etc. in addition to non-adhesiveness, lubricity, blocking resistance, etc. .

Patent applicant: Dainichiseika Industrial Co., Ltd. (1 other person)

Claims (2)

[Claims] (1) A resin characterized by being made by copolymerizing a siloxane compound having an active hydrogen group and a lactone compound, and consisting of a siloxane-modified polyester resin and a vinyl chloride resin that do not substantially contain unreacted siloxane compounds. Composition. (2) The resin composition according to claim 1, wherein the siloxane segment accounts for 5 to 80% by weight in the copolymer.