JPH0314069B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a matte thermoplastic resin composition,
More specifically, it is a matte thermoplastic resin with excellent weather resistance, chemical resistance, etc., consisting of an acrylic multilayer structure polymer with a crosslinked elastic material as its core, a fluorine-based polymer, and a polymer matting agent. The present invention relates to a composition. Moldings made of resins that have some drawbacks in weather resistance, such as vinyl chloride resin, ABS resin, and polycarbonate resin,
Alternatively, attempts have been made to improve the weather resistance of various molded objects such as PVC steel plates or PVC wallpaper coated with these resins by coating them with an acrylic resin composition having excellent weather resistance; Many attempts have been made to improve their chemical resistance and stain resistance by coating them with resin compositions that have excellent chemical resistance and stain resistance. However, it is compatible with the above-mentioned flexibility, toughness, workability, adhesion, etc. required for the coating material of such acrylic resin compositions, as well as the above-mentioned objectives such as stain resistance, chemical resistance, weather resistance, etc. The reality is that it is not easy to do so, and many of the above attempts have not necessarily been successful. In particular, for housing interior materials such as wallpaper or housing equipment such as home appliances, matte surfaces are generally preferred, but the above-mentioned acrylic resin compositions are originally high-gloss resins. Therefore, it is difficult to meet such demands. That is, for example, it is difficult to obtain a sufficiently matte state by surface embossing using a calendar roll, which is generally performed when producing the above-mentioned PVC wallpaper. On the other hand, there is a method in which an acrylic resin composition is mixed with a certain matting agent, most commonly an inorganic substance such as calcium carbonate or silica, and then coated. The resin composition significantly reduces properties such as flexibility and toughness and its processability,
As a result, there is an unavoidable problem that it becomes more difficult to achieve both the above-mentioned flexibility, processability, etc., stain resistance, weather resistance, and matte effect. In view of the current situation, the inventors aimed to obtain an acrylic resin composition suitable for a coating material or coating film material that has the above-mentioned flexibility, processability, stain resistance, weather resistance, matte property, etc. As a result of intensive studies, we found that a blend of an acrylic multilayer structure with a crosslinked acrylic elastic material as its core and a fluoropolymer, which will be described in detail later, was selected from the group of aromatic vinyl monomers and alkyl (meth)acrylates. The present invention was achieved by discovering that a resin composition containing a moderately crosslinked polymer matting agent containing at least one selected monomer as a main component satisfies this objective. That is, the present invention comprises 1 to 99 parts by weight (hereinafter abbreviated as "parts") of a multilayer structure polymer () having the structure shown below, and the general formula CF ₂ =CXY (wherein X, Y are H,
A homopolymer of a monomer (representing F, Cl, CF ₃ ) or a copolymer consisting of two or more of these monomers, or a proportion of these monomers of 50% by weight
(hereinafter abbreviated as %) Thermoplastic material consisting of 1 to 99 parts of at least one fluorine-based polymer selected from the group consisting of copolymers with other copolymer monomers (hereinafter abbreviated as %) This is a matte thermoplastic resin composition prepared by blending 1 to 70 parts of a polymer matting agent () having the structure shown below to 100 parts of the resin composition. [Acrylic multilayer structure polymer ()] 60 to 100 parts of alkyl acrylate (A ₁ ) having an alkyl group having 8 or less carbon atoms, 0 to 40 parts of (A ₁ ) and 1 double bond that can be copolymerized. a monomer other than (A ₁ ) (A ₂ ), 0 to 10 parts of a polyfunctional crosslinking monomer (A ₃ ), based on 100 parts of the total amount of (A ₁ ) to (A ₃ ) above. 0.1
An innermost layer polymer (A) consisting of ~5 parts of a grafting cross-agent, having a gel content of 60% or more, a swelling degree of 15 or less, and accounting for 5 to 80% in the polymer (); , 51 to 100 parts of alkyl methacrylate (B ₁ ) having an alkyl group having 4 or less carbon atoms, 0 to 49 parts of a monomer other than (B ₁ ) having one double bond that can be copolymerized with (B ₁ ); an outermost layer polymer (B) having a glass transition temperature (Tg) of at least 60° C. and having a composition of polymer (B ₂ ), and having an amount of 10 to 85% in the polymer (); As a basic structural unit, between the polymer (A) layer and the polymer (B) layer, an alkyl methacrylate (C ₁ ) having 10 to 90 parts of an alkyl group having 4 or less carbon atoms, and 10 to 90 parts of an alkyl group having 8 carbon atoms; Alkyl acrylate (C ₂ ) having the following alkyl group, other than (C 1 ), (C ₂ ) having one double bond that can be copolymerized with 0 to 20 parts of (C ₁ ), (C _{2 )} Monomer ( _C3 ), 0 to 10 parts of polyfunctional crosslinking monomer ( _C4 ), 0.1 to 100 parts of the total amount of the above ( _C1 ) to ( _C4 )
An acrylic multilayer structure polymer () capable of having at least one intermediate layer (C) consisting of 5 parts of a graft cross-agent. [Polymer matting agent ()] 10 to 100 parts of alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, 0 to 60 parts of an alkyl acrylate having an alkyl group having 1 to 13 carbon atoms, 0 to 90 parts % aromatic vinyl monomer, 0 to 40 parts of other monoethylenically unsaturated monomer, A polymer matting agent () having an average particle diameter of 1 to 500μ obtained by polymerizing a crosslinkable monomer having a double bond. In addition, in the acrylic multilayer structure polymer [], a polyfunctional crosslinking monomer is a monomer that has at least two double bonds with equal reactivity and is effective in crosslinking the layer itself containing it. It is something that works;
It does not affect interlayer bonding with other layers.
Moreover, the graft cross-agent has at least two double bonds with different reactivities. In the present invention, the acrylic multilayer structure polymer () contains 10 to 70% of the innermost layer polymer (A),
It consists of an intermediate layer polymer (C) of 5 to 40% and an outermost layer polymer (B) of 10 to 85%, and the ratio of alkyl acrylate in each layer varies from the innermost layer polymer (A) to the outermost layer polymer (B). It is most preferable to make it monotonically decreasing toward coalescence. The present invention will be explained in detail below, but first, the acrylic multilayer structure polymer used in the present invention will be explained in more detail. The innermost layer polymer (A) constituting the acrylic multilayer structure polymer (2) imparts flexibility and toughness to the polymer (2). The alkyl acrylate (A ₁ ) having an alkyl group having 8 or less carbon atoms forming the polymer (A) is at least one of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. Used within the scope of the section. The lower the glass transition temperature (Tg) of the homopolymer is, the more advantageous it is. Monomers (A ₂ ) other than (A ₁ ) having one copolymerizable double bond include those copolymerizable with the alkyl acrylate (A ₁ ), such as lower alkyl methacrylate, lower alkoxy acrylate, and cyanoethyl. (Meth)acrylic acid derivatives such as acrylate, acrylamide, acrylic acid, and methacrylic acid are preferred, and others such as styrene,
Examples include alkyl-substituted styrene, acrylonitrile, methacrylonitrile, etc., and are used in an amount of 0 to 40 parts. Furthermore, the polyfunctional crosslinking monomer (A ₃ ) has two or more copolymerizable double bonds, for example,
Alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate, 1,3 butylene glycol dimethacrylate, 1,4 butylene glycol dimethacrylate and propylene glycol dimethacrylate are preferred, and polyvinylbenzenes such as divinylbenzene and trivinylbenzene, alkylene glycol diacrylates, etc. is also available. These monomers act effectively to bridge the layer in which they are contained, but do not act on bonding between layers with other layers. Even if the polyfunctional crosslinking monomer (A ₃ ) is not used at all, a fairly stable multilayer structure polymer can be obtained as long as the grafting agent is present, but it can be used as desired depending on the required physical properties. Amounts range from 0 to 10 parts by weight. On the other hand, a grafting agent has two or more double bonds with different reaction rates, such as copolymerizable α,β-unsaturated monocarboxylic acid or dicarboxylic acid allyl, methallyl or crotyl ester, preferably acrylic acid. Allyl esters of , methacrylic acid, maleic acid and fumaric acid are used, with allyl methacrylate being particularly effective. In addition, triallyl cyanurate, triallyl isocyanurate, etc. can also be effectively used. Such graft cross-agents are chemically bonded primarily because the conjugated unsaturated bonds of the ester react much faster than allyl, methallyl, or crotyl groups. During this time, a substantial portion of the allyl group, methallyl group, or crotyl group acts effectively during the polymerization of the next layer to provide a graft bond between two adjacent layers. If the amount of graft cross-agent used is less than 0.1 part, the effective amount of graft bonding is too small, and when the final polymer is molded, layer destruction will easily occur, resulting in a significant decrease in transparency, etc. . Moreover, if the amount exceeds 5 parts, the elasticity is particularly deteriorated, and sufficient flexibility and toughness cannot be imparted. The amount of the innermost layer polymer (A) in the acrylic multilayer structure polymer () is 5 to 80%, preferably 10%.
~70%. If the amount is less than the lower limit of 5%, the desired flexibility and toughness cannot be imparted to the acrylic multilayer structure polymer. In addition, if the amount exceeds 80%, the acrylic multilayer structure polymer () itself becomes rubbery and becomes difficult to handle.
Various physical properties such as transparency are also significantly reduced. The innermost layer polymer (A) made of a crosslinked elastic body of acrylic rubber can have a two-stage structure or a three-stage structure, if necessary. Furthermore, the innermost layer polymer (A) has preferable ranges in terms of gel content, degree of swelling, particle size, etc., in addition to the above. The amount is 60% or more, preferably 80% or more, and the degree of swelling is 15 or less, preferably 3 to
Must be in the range of 15. The gel content and degree of swelling are controlled within preferred ranges by adjusting the amounts of the polyfunctional monomer and grafting agent used. As the use of the above polyfunctional monomers and grafting cross-agents increases, the gel content becomes higher;
Conversely, the degree of swelling decreases. If the gel content is less than 60% or the degree of swelling is higher than 15, the elastic particles in the composition may re-agglomerate or deform in the flow direction of the resin during molding, resulting in uneven impact strength. or weather resistance may deteriorate. (Method for measuring gel content and degree of swelling) A predetermined amount of the polymer was sampled according to JIS K-6388, and methyl ethyl ketone (hereinafter referred to as
(abbreviated as MEK) to raise the degree of swelling, wipe off the adhered MEK, and measure its weight.
After that, MEK is removed by drying in a vacuum dryer, and the absolute dry weight, which has reached a constant weight, is read and calculated using the following formula. Swelling degree = Weight after MEK swelling - Bone dry weight / Bone dry weight Gel content (%) = Bone dry weight / Weight of collected sample x 10
0 The particle size of the innermost layer polymer (A) is 500 to 5000
Within the range of Å, the transparency and stress whitening resistance of the final multilayer polymer () will not be significantly reduced. Next, alkyl methacrylate (B ₁ ) having an alkyl group having 4 or less carbon atoms forms the outermost layer polymer (B) constituting the acrylic multilayer structure polymer ().
At least one of methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate is used in an amount of 51 to 100 parts, with methyl methacrylate being particularly preferred. Monomers (B ₂ ) other than (B ₁ ) having one copolymerizable double bond include alkyl acrylates having an alkyl group having 8 or less carbon atoms, as well as those shown in the component (A ₂ ) above. Can be mentioned. These (B ₂ ) components are used in a range of 0 to 49 parts. The outermost polymer layer (B) is essentially a resin layer and its Tg is 60
The temperature must be above ℃. The glass transition temperature (Tg) of the outermost layer polymer (B) used in this specification including the present examples is given in the Polymer Handbook, 2nd edition (A WILEY-
(B ₁ ), which constitutes the outermost layer polymer (B), as described in INTERSCIENCE PUBLICATION),
From the Tg of each polymer in (B ₂ ) and its composition ratio,
It was calculated using the following Fox formula described in Basics and Applications of Polymer Alloys (edited by The Society of Polymer Science, published by Tokyo Kagaku Dojin). Furthermore, polymethyl methacrylate (PMMA) is
Three types of Tg are described depending on the stereoregularity of the polymer, but in the case of PMMA of the present invention, the value of attack tick was used assuming that it was not crystallized. In addition, the Tg of the polymer obtained by polymerizing monomers not listed in the above-mentioned Polymer Handbook 2nd Edition or monomers that cannot be uniquely identified from this Polymer Handbook 2nd Edition, It was determined using a dynamic mechanical analyzer. Tg ^-1 = ω ₁ Tg ₁ ^-1 + ω ₂ Tg ₂ ^-1 Tg; Glass transition temperature of copolymer Tg ₁ , Tg ₂ ; Glass transition temperature of each component ω ₁ , ω ₂ ; Weight fraction of each component Maximum When the Tg of the outer layer polymer (B) is less than 60°C, the solvent resistance of the multilayer structure polymer () itself deteriorates, which is not preferable. The amount of the outermost layer polymer (B) in the acrylic multilayer structure polymer () is 10 to 85%, preferably 20 to 85%.
It is 70%. If the amount is less than 10%, a stable polymer cannot be obtained from the viewpoint of polymerization and coagulation operations. Also 85%
If the amount exceeds this amount, the content of the innermost layer polymer (A) will be too small to obtain the desired elasticity. Incidentally, during the polymerization of the outermost layer polymer (B), it is also possible to adjust the degree of polymerization using a chain transfer agent or the like, and this is often preferable. The acrylic multilayer structure polymer () used in the present invention is the above-mentioned innermost layer polymer (A) and outermost layer polymer (B).
is the basic structural unit, but in order to further increase the affinity between the polymer (A) layer and the polymer (B) layer, there is a structure between the polymer (A) layer and the polymer (B) layer. 10 to 90 parts of alkyl methacrylate (C ₁ ) having an alkyl group of up to 4 carbon atoms, 90 to 10 parts of an alkyl acrylate (C ₂ ) having an alkyl group of up to 8 carbon atoms, 0 to
20 parts of monomers other than (C ₁ ) and (C ₂ ) having one copolymerizable double bond (C ₃ ), 0 to 10 parts of polyfunctional monomers (C ₄ ), these The ratio of alkyl acrylate in each layer is from layer ₍ A ₎ to layer (B). It is possible that at least one layer is arranged in a monotonically decreasing manner, and it is more preferable to have a three-layer structure including one such intermediate layer. Here (C ₁ )
The components and grafting agent for (C ₄ ) are the same as those used in the polymers (A) and (B). It is essential to use the above-mentioned graft cross-agent in this intermediate layer (C), and if it is not used, the multilayer structure polymer will easily whiten when subjected to stress, and desired physical properties will not be obtained. I can't.
A particularly preferable amount of grafting agent is
0.5 per 100 parts of the total amount of other monomers constituting (C)
~2 parts. The amount of this intermediate layer (C) in the acrylic multilayer structure polymer () is 70% or less, preferably 5 to 5%.
40%, and if it exceeds 70%, the overall balance of the final polymer will be disturbed, which is not preferable. Next, the outermost layer polymer (B) and the middle layer polymer (C)
must be grafted to the innermost layer polymer (A) to some extent, and it is preferable that the grafting ratio value based on the measurement method below is 25% or more. (Method for measuring graft ratio) Weigh 0.5 g of sample into a 100 ml Erlenmeyer flask.
After adding 50 ml of MEK and leaving it for a day and night, the mixture is separated into soluble and insoluble components using a centrifuge. The insoluble content is dried under reduced pressure to a constant weight, and the weight is measured, and this is calculated as the graft rubber content using the formula below. Grafting ratio (%) = Graft rubber content - Amount of crosslinked elastic body component / Amount of crosslinked elastic body component x 100 The above acrylic multilayer structure polymer () can be easily obtained by a sequential multistage polymerization method using a normal emulsion polymerization method. It will be done. That is, the innermost layer polymer (A) is first obtained by an emulsion polymerization method, and then the next layer is polymerized in the presence of the innermost layer polymer (A). In this case, no emulsifier is added that would cause new polymer particles to be formed. Thereafter, this process is repeated to complete the polymerization of the multilayer structure polymer (). Emulsifiers, catalysts used during this polymerization,
Coagulants and the like are not particularly regulated. Note that an emulsion suspension polymerization method in which only the outermost layer polymer (B) is converted to suspension polymerization after emulsion polymerization is also an advantageous method. Next, the fluorine-based polymer () used in the present invention has the general formula CF ₂ =CXY (wherein X, Y is H,
Homopolymers of monomers represented by (F, Cl, CF ₃ ), or copolymers consisting of two or more of these monomers, or those in which the ratio of these monomers is 50% or more. At least one type of polymer selected from the group consisting of copolymers with other copolymerizable monomers, specifically polyvinylidene fluoride, polytetrafluoroethylene, polyfluorochloroethylene, polytetrafluoroethylene and vinylidene fluoride copolymer,
A typical example is a copolymer of tetrafluoroethylene and hexafluoropropylene. Among these, polyvinylidene fluoride and a copolymer of ethylene tetrafluoride and vinylidene fluoride are particularly preferred. The blending ratio of the acrylic multilayer structure polymer () and the fluoropolymer () can be arbitrarily selected within the range of 1/99 to 99/1 depending on the required properties. It is preferable that the ratio of the structural polymer () is 51% or more from the viewpoint of adhesion to the base material when used as a coating material. Furthermore, the matting agent () used in the present invention
It is not just a matter of having a matte effect, but also a combination of the above-mentioned acrylic multilayer structure polymer () and fluorine-based polymer, which serve as the base polymer, in terms of weather resistance, stain resistance, flexibility, toughness, and processing properties. It should not impair the characteristics of the blend composition with the polymer. As a matting agent () satisfying these conditions, 10 to 100 parts of alkyl methacrylate whose alkyl group has 1 to 4 carbon atoms, 0 to 60 parts of an alkyl acrylate whose alkyl group has 1 to 13 carbon atoms, 0 to 60 parts of an alkyl acrylate whose alkyl group has 1 to 13 carbon atoms, ~
A non-crosslinkable monomer consisting of 90 parts of an aromatic vinyl monomer, 0 to 40 parts of other monoethylenically unsaturated monomers, and 0.5 to 5 parts of two or more monomers in the molecule per 100 parts of the non-crosslinkable monomer. It is necessary that the matting agent is a polymeric matting agent () having an average particle diameter of 1 to 500 μm obtained by polymerizing a crosslinkable monomer having a double bond. In this matting agent (2), the amount of crosslinking monomer added is particularly important, and it is specifically used in a range of 0.5 to 5 parts per 100 parts of non-crosslinking monomer, but a range of 1.5 to 4 parts is particularly preferred. In other words, if the amount of the crosslinking monomer is less than 0.5 part, sufficient crosslinking will not be obtained to show a sufficient matting effect, and conversely, if it is used in excess of 5 parts, there will be too much crosslinking and it will not be compatible with the resin. None of these methods are suitable because they lower the solubility and lower the processability and physical properties of the polymer that becomes the matrix. In this case, as the crosslinking monomer, a compound having two or more double bonds in the molecule is used, and in particular, a compound in which at least one of the two or more double bonds is an allyl group is used. This is particularly preferred from the viewpoint of controlling the degree of crosslinking. Typical crosslinking monomers containing such an allyl group include allyl methacrylate, triallyl cyanurate, and triallyl isocyanurate. In addition, ordinary polyfunctional monomers such as unsaturated carboxylic acid esters of alkylene glycol, unsaturated alcohol ethers of alkylene glycol, and polyvalent vinylbenzenes can also be used as the crosslinking monomer. The non-crosslinking monomer used in the production of the above matting agent () is 10 to 100 parts, preferably 10 parts.
~95 parts of alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, 0 to 60 parts, preferably 3
~40 parts of alkyl methacrylate having an alkyl group having 1 to 13 carbon atoms, 0 to 90 parts, preferably 1
~70 parts of aromatic vinyl monomer and 0 to 40 parts, preferably 0 to 20 parts of other monoethylenically unsaturated monomers are used. As the alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, methyl methacrylate is typical, and ethyl methacrylate and butyl methacrylate can also be used. In addition, as the alkyl acrylate having an alkyl group having 1 to 13 carbon atoms,
Ethyl acrylate, butyl acrylate, 2-
Typical examples include ethylhexyl acrylate. Furthermore, although styrene is a typical aromatic vinyl monomer, vinyltoluene, α-methylstyrene, halogenated styrene, etc. can also be used. Other monoethylenically unsaturated monomers include fumaric acid, maleic acid, copolymerizable carboxylic acids and their esters, (meth)acrylic acid,
Vinyl halides, vinyl esters, acrylonitrile, etc. are used. In addition, the particle size of the matting agent () used in the present invention is also a major constituent factor,
Usually particles with a diameter of 1 to 500μ are used,
Particularly preferred are those with a diameter of 40 to 200μ. If the particle size is less than 1μ, sufficient matting effect cannot be obtained, and if the particle size exceeds 500μ, the film forming properties of the base material will be significantly reduced, and only a film with an extremely rough surface will be obtained. . Such a matting agent can be easily produced by ordinary suspension polymerization, but the production method is not limited to this, and as long as the constituent requirements such as particle size are satisfied, there is no problem in the polymerization recipe. There are no restrictions. The amount of the above-mentioned matting agent () added is 1 to 70 parts per 100 parts of the blend composition of the above-mentioned multilayer structure polymer and fluorine-based polymer (2), but it is usually effective even if it is 20 parts or less. is often sufficient. And these acrylic multilayer structure polymers (),
The fluorine-based polymer () and the matting agent () can be mixed by a normal mixing method such as using a Henschel mixer, but the acrylic multilayer structure polymer () and the fluorine-based polymer () can be mixed. It is more preferable to heat the three to a temperature higher than the softening point of both and then mechanically mix the mixture in that state. Any suitable mixing method will generally be used, such as kneading, mixing in a heated high shear mixing device, such as a Burberry type mixer. In addition, other usual additives such as antioxidants, ultraviolet absorber fillers, pigments, etc. can be added to the resin composition of the present invention, if necessary, and also without deteriorating the physical properties. It is also possible to appropriately blend other polymers within the range. The resin composition of the present invention obtained in this way is
It can be easily formed into a film or sheet by a conventional method such as a T-die method, an inflation method, or a calendar method, or it can also be directly extruded and coated onto a substrate. Furthermore, these films can be easily printed and their design effects can be significantly enhanced. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not necessarily limited thereto. Note that all parts in each example are based on weight. Abbreviations in Examples are as follows. Methyl methacrylate MMA Butyl acrylate BuA Styrene St 1,3-Butylene dimethacrylate BD Allyl methacrylate AMA Cumene hydroperoxide CHP n-Octyl mercaptan n-OSH Lauroyl peroxide LPO Methyl ethyl ketone MEK Di-n-Octyl phthalate DOP Azobisisobutyl nitrile AIBN Polyvinyl Alcohol PVA Example 1 (1) In a reaction vessel equipped with a condenser, add 250 parts of ion-exchanged water,
1 part sulfosuccinate sodium salt, 0.05 sodium formaldehyde sulfoxylate
After stirring under nitrogen flow, 29 parts of
Charge a monomer mixture consisting of BuA, 1 part BD and 0.15 part AMA. In the above BuA
Dissolve 0.1% CHP in the total amount of BuA and BD. All monomers added in subsequent steps also contain 0.1% CHP for each monomer unless otherwise specified. The temperature of the reaction vessel is raised to 50° C. under a nitrogen gas flow with stirring at a rotational speed of 200 rpm, and the temperature is maintained at 50° C. while stirring for 120 minutes to complete the polymerization of the innermost layer polymer (A). Next, the reaction system was heated to 75℃ and 10 parts of
Intermediate layer components consisting of MMA, 10 parts BuA, and 0.1 part AMA are added over 40 minutes and held for an additional 40 minutes to complete polymerization of the intermediate layer (C). lastly
47.5 parts MMA, 2.5 parts BuA and 0.1 parts n-
The outermost layer polymer component consisting of OSH was added over 60 minutes and held for an additional 60 minutes to complete the polymerization of the outermost layer (B), resulting in an acrylic multilayer structure polymer (-(a)) consisting of three layers. was manufactured. The innermost layer polymer (A) of this acrylic multilayer structure polymer (-(a)) has a gel content of 89% and a swelling degree of 5.5.
The particle size was approximately 1500 Å, and the total gel content was 65%. The latex of this acrylic multilayer structure polymer (-(a)) was salted out using 5 parts of calcium chloride, filtered and washed with water, and then dried to obtain a dry powder. (2) Production of matting agent (2) Charge the following compound into a reaction vessel similar to that used in (1). St 60 parts MMA 20〃 BuA 20〃 AMA 3〃 n-OSH 0.1〃 AIBN 2〃 Tertiary calcium phosphate 2〃 Water 200〃 After sufficiently replacing the inside of the container with nitrogen gas, the mixture of the above compounds was heated to 75℃ while stirring. and proceed with polymerization in nitrogen gas. 85 after 3 hours
The temperature was raised to 0.degree. C. and held for 3 hours, then raised to 95.degree. C. and held for 1 hour to complete polymerization. After cooling, it was dehydrated and dried to obtain granular beads (matting agent - (a)). The weight average particle diameter of the beads obtained was approximately 70 μ, the degree of swelling in MEK was 12, and the gel content was 65%. (3) 80 parts of the acrylic multilayer structure polymer (-(a)) produced in (1) above, 20 parts of polyvinylidene fluoride (Kynar 901, Pennwalt), and the polymer matting agent produced in (2) above. 10 parts and 1 part UV absorber
The mixture was blended using a Henschel mixer and shaped into pellets using an extruder with a screw of 40 mmφ. After sufficiently drying the pellets, a film having a thickness of 80 μm was formed by an inflation method. The tensile strength of this film is 310Kg/cm ² ,
The tensile elongation at break was 140%, and the 60 degree specular gloss was 25. This film was attached to a galvanized 0.5 mm cold-rolled steel plate using a commercially available adhesive and subjected to a 3000-hour accelerated exposure test using a Sunshine Weather-Ometer, but no change in appearance was observed even after exposure. It showed excellent weather resistance. Reference example 1 When 80 parts of acrylic multilayer structure polymer (-(a)), 20 parts of polyvinylidene fluoride, and 1 part of ultraviolet absorber are blended, and the above matting agent (-(a)) is not blended. The film obtained in the same manner as in Example 1 showed good film physical properties such as a tensile strength of 320 Kg/cm ² and a tensile elongation at break of 165%.
The resin composition had a high specular gloss of 120, which was not the matte resin composition targeted by the present invention. Comparative Example 1 A film was formed in the same manner as in Example 1, except that commercially available calcium carbonate was used instead of the polymer matting agent (-(a)). The resulting film had a rough appearance, insufficient matteness (60 degree specular gloss of 65), and was brittle (tensile elongation at break 25%). Reference example 2 100 parts of acrylic multilayer structure polymer (-(a)),
A film obtained in the same manner as in Example 1 when only 10 parts of the polymer matting agent (-(a)) and 1 part of the ultraviolet absorber were blended and the above fluorine-based polymer () was not blended. The appearance was relatively good and the matte effect was sufficient (60 degree specular gloss level 28), but the tensile strength was 260 Kg/cm ² and the tensile elongation at break was 75%.
The physical properties of the film were significantly inferior. Comparative Example 2 A film with a thickness of approximately 80 μm was formed using the same procedure as in Example 1, except that no grafting agent was used during the polymerization of the innermost layer (A) and intermediate layer (C) of the acrylic multilayer structure polymer. It was filmed. The obtained film had a poor appearance and a low tensile strength value of 60%. Furthermore, this film easily whitens upon impact, and even in an accelerated exposure test using a Sunshine Weatherometer, it shows yellowing and a significant decrease in tensile strength, resulting in poor weather resistance and lack of the excellent luster that is the objective of the present invention. It did not become an erasable resin composition. Example 2 The following compounds were charged into the reaction vessel used in Example 1, and after the inside of the vessel was sufficiently replaced with nitrogen gas, polymerization was carried out at 85°C for 2 hours with stirring, and then at 95°C for 30 hours.
Polymerization was completed by heat treatment for several minutes, and after cooling, dehydration and drying were performed to obtain matting agents ()-(b). MMA 60 parts BuA 35〃 St 5〃 AMA 2〃 n-OSH 0.2〃 LPO 2〃 PVA 2〃 Water 200〃 The average particle size of the obtained matting agent ()-(b) is approximately
80μ, gel content 75%, and swelling degree 10. A film was obtained in the same manner as in Example 1, except that 10 parts of the matting agent (-(a)) was replaced with each part of the matting agent (-(b)) as shown in Table 1 below.
The values of 60 degree specular gloss and tensile elongation were measured and the results are shown in Table 1.

[Table] Example 3 90 parts of the acrylic multilayer structure polymer (-(a)) produced in Example 1, 10 parts of a copolymer of vinylidene fluoride and ethylene tetrafluoride (Kynar 7201, Pennwalt Co.), 10 parts of the polymer matting agent (-(a)) produced in Example 1 and 1 part of the ultraviolet absorber were blended in a Henschel mixer, and then shaped into pellets using an extruder with a screw of 40 mmφ. After the pellets were sufficiently dried, they were formed into a film with a thickness of 50 .mu.m by the T-die method using the same extruder. This film had a tensile strength of 305 Kg/cm ² , a tensile elongation at break of 160%, and a 60 degree specular gloss of 28. This matte film was heat-pressed onto a commercially available PVC wallpaper by passing it between two rolls heated to 120°C with a linear pressure of about 10 kg/cm. The weather resistance of the resulting wallpaper was evaluated by an accelerated exposure test using a fade meter in comparison with conventional wallpaper that was not laminated with a matte film. Commercially available matte film that is not laminated
The PVC wallpaper turned yellow after 100 hours, but no change was observed in the matte film coated PVC wallpaper of this example even after 300 hours. Example 4 (1) Into the reaction vessel used in Example 1-(1), 250 parts of ion-exchanged water, 1.5 parts of sulfosuccinic acid ester sodium salt, and 0.05 parts of sodium formaldehyde sulfoxylate were charged and heated under a stream of nitrogen. After stirring at 58 parts BuA, 2 parts BD, 0.3 parts
0.1% of the total amount of AMA, BuA and BD
Charge a monomer mixture consisting of CHP. The temperature of the reaction vessel was raised to 50° C. while stirring under a nitrogen gas flow, and the temperature was maintained for 180 minutes to complete the polymerization of the innermost layer polymer (A). This innermost layer polymer
The gel content of (A) is 91%, the degree of swelling is 5.3,
The particle size was 1300 Å. Next, the reaction system was heated to 75°C, 5 parts of MMA,
5 parts BuA, 0.05 parts AMA and MMA and BuA
A monomer mixture consisting of 0.1% CHP was added over a period of 30 minutes to the total amount of , and this state was maintained for an additional 30 minutes to polymerize the intermediate layer (C), followed by addition of 27 parts of MMA and 3 parts of CHP. BuA and these
A monomer mixture consisting of 0.1% CHP was added over 60 minutes, and the state was maintained for an additional 60 minutes to polymerize the outermost layer (B) to form an acrylic multilayer structure polymer (-(b) ) polymerization was completed. This acrylic multilayer structure polymer (-(b))
The gel content was 80%. This latex was salted out using 5 parts of calcium chloride, filtered, washed with water, and dried to obtain a dry powder. (2) 80 parts of the acrylic multilayer structure polymer (-(b)) produced in (1) above and 20 parts of vinylidene polyfluoride,
Pellets were obtained in the same manner as in Example 1 by blending 10 parts of a polymer matting agent and 1.5 parts of an ultraviolet absorber. Using this pellet, a laminated film was obtained by coextrusion with a semi-rigid vinyl chloride resin (containing 20 parts of DOP) (PVC 100μ, acrylic 100μ). The 60 degree specular gloss on the PVC side of the obtained laminated film was high at 90, but that on the resin composition side of the present invention was sufficiently low at 31, giving a uniformly matte state. When this laminated film was subjected to an accelerated exposure test using a Sunshine Weatherometer, the sample with the PVC side exposed completely discolored and lost its luster after 500 hours, but the resin of the present invention Regarding the composition, no discoloration or fading was observed even after 3000 hours, and no migration of the plasticizer to the film surface was observed. Example 5 20 parts of the acrylic multilayer structure polymer (-(a)) produced in Example 1, vinylidene fluoride (Kynar)
731, Pennwalt Co.), 10 parts of the polymer matting agent (-(a)) prepared in Example 1, and 1 part of the ultraviolet absorber, and a film was obtained in the same manner as in Example 1. Its 60 degree specular gloss is 29, and its tensile strength is
The weight was 430Kg/cm ² and the tensile elongation at break was 210%. Example 6 A multilayer structure polymer [-(c)] was obtained by carrying out polymerization in the same manner as in Example 1-(1), except that the composition of the multilayer structure polymer [] was changed as shown in Table 2 below. . This acrylic multilayer structure polymer [-(c)]50
50 parts of polyvinylidene fluoride (Kynar 721, Pennwalt Co., Ltd.), 10 parts by weight of the polymer matting agent [-(a)] produced in Example 1-(2), and 2 parts of the ultraviolet absorber. 80μ using the same procedure as Example 1-(3).
When a film was formed, the tensile strength of the film was 370 Kg/cm ² , the tensile elongation at break was 190%, and the 60 degree specular gloss was 26. This film was attached to a galvanized 0.5 mm cold-rolled steel plate using a commercially available adhesive and subjected to a 3000-hour accelerated exposure test using a Sunshine Weather-Ometer, but no change in appearance was observed even after exposure. It showed excellent weather resistance.

[Table] Example 7 The following compounds were charged into the reaction vessel used in Example 1, and after the inside of the vessel was sufficiently replaced with nitrogen gas, polymerization was carried out at 85°C for 2 hours with stirring, and then at 95°C for 30 hours.
Polymerization was completed by heat treatment for several minutes, and after cooling, dehydration and drying were performed to obtain a matting agent ()-(c). MMA 100 parts AMA 1〃 n-OSH 0.2〃 LPO 2〃 PVA 4〃 Water 200〃 The average particle size of the obtained matting agent ()-(c) is approximately
60μ, gel content 80%, and swelling degree 2. A film was obtained in the same manner as in Example 1, except that 10 parts of the matting agent (-(c)) was used instead of 10 parts of the matting agent (-(a)). Its 60 degree specular gloss is 29,
The tensile strength was 320 Kg/cm ² and the tensile elongation at break was 105%.

Claims (1)

[Claims] 1 1 to 99 parts by weight of a multilayer polymer () having the structure shown below, and the general formula CF ₂ =CXY (wherein X and Y represent H, F, Cl, and CF ₃ ) A homopolymer of a monomer having
At least one selected from the group consisting of copolymers with other copolymer monomers having a polymerization percentage of 50% or more
1 to 70 parts by weight of a polymer matting agent (2) having the structure shown below is blended to 100 parts by weight of a thermoplastic resin composition consisting of 1 to 99 parts by weight of a fluorine-based polymer (2). Matte thermoplastic resin composition. [Acrylic multilayer structure polymer ()] 60 to 100 parts by weight of an alkyl acrylate (A ₁ ) having an alkyl group having 8 or less carbon atoms, and 0 to 40 parts by weight of a double bond copolymerizable with (A ₁ ) A monomer other than (A ₁ ) having one (A ₂ ), 0 to 10 parts by weight of a polyfunctional crosslinking monomer (A ₃ ), the total amount of the above (A ₁ ) to (A ₃ ) 100 Per weight part
The gel content is 60% by weight or more and the swelling degree is 15 or less, consisting of 0.1 to 5 parts by weight of a grafting cross-agent,
and an innermost layer polymer (A) that accounts for 5 to 80% by weight in the polymer (), and an alkyl methacrylate (B ₁ ) having an alkyl group having 4 or less carbon atoms in an amount of 51 to 100 parts by weight, 0 ~49 parts by weight of a monomer (B ₂ ) other than (B ₁ ) having one double bond copolymerizable with (B ₁ ), with a glass transition temperature of at least 60°C
and the amount occupied in the polymer () is 10
~85% by weight of the outermost layer polymer (B) as a basic structural unit, and between the polymer (A) layer and the polymer (B) layer, 10 to 90 parts by weight of an alkyl group having 4 or less carbon atoms. Copolymerizable with 10 to 90 parts by weight of alkyl acrylate (C _{2 )} having an alkyl group having 8 or less carbon atoms, and 0 to 20 parts by weight of (C ₁ ) and (C ₂ ). A monomer other than (C ₁ ) and (C ₂ ) having one double bond (C ₃ ), 0 to 10 parts by weight of a polyfunctional crosslinking monomer (C ₄ ), the above (C ₁ ) to (C ₄ ) per 100 parts by weight
Intermediate layer consisting of 0.5 to 5 parts by weight of graft cross-agent
An acrylic multilayer structure polymer () which can have at least one layer of (C). [Polymer matting agent ()] 10 to 100 parts by weight of alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, 0 to 60 parts by weight of an alkyl acrylate having an alkyl group having 1 to 13 carbon atoms, 0 ~90 parts by weight of an aromatic vinyl monomer, 0 to 40 parts by weight of other monoethylenically unsaturated monomers, and 0.5 to 5 parts by weight per 100 parts by weight of the non-crosslinkable monomer in the molecule. A polymer matting agent () having an average particle diameter of 1 to 500μ obtained by polymerizing a crosslinkable monomer having two or more double bonds. 2. The gloss according to claim 1, wherein the fluorine-based polymer () according to claim 1 is essentially polyvinylidene fluoride or a copolymer of vinylidene fluoride and tetrafluoroethane. Erasable thermoplastic resin composition. 3 Acrylic multilayer structure polymer () of item 1 above
is 51 to 95% by weight, and fluorine-based polymer () is 5 to 49% by weight.
The matte thermoplastic resin composition according to claim 1, characterized in that the proportion is in % by weight.