JPS5989344A - Matte thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To prepare the titled composition having excellent weather resistance, chemical resistance, etc., and useful as a coating material, etc., by compounding a specific polymeric matting agent to a blend of a fluorine polymer and an acrylic multi-layered structure having a crosslinked acrylic elastomer as a core. CONSTITUTION:The objective composition is prepared by compounding (A) 1- 99pts.wt. of an acrylic polymer having multi-layered structure consisting of (i) the innermost polymer composed of 60-100pts.wt. of a 1-8C alkyl acrylate, etc., (ii) the outermost polymer composed of 51-100pts.wt. of 1-4C alkyl methacrylate, etc., and (iii) an intermediate layer composed of 10-90pts.wt. of a 1- 4C alkyl methacrylate, etc. and intermposed between the layers (i) and (ii) with (B) 1-99pts.wt. of a fluorine polymer composed of the (co)polymer of the monomer of formula CF2=CXY (X and Y are H, F, Cl or CF3), etc., and compounding 100pts.wt. of the above resin composition with (C) 1-70pts.wt. of a polymeric matting agent composed of an aromatic vinyl monomer, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a matting thermoplastic resin composition, and more specifically, the present invention relates to a matting thermoplastic resin composition, and more specifically, it comprises a matting thermoplastic resin composition comprising an acrylic multilayer structure polymer having a crosslinked elastomer as a core, a fluoropolymer, and a polymer matting agent. The present invention relates to a matte thermoplastic resin composition having excellent weather resistance, chemical resistance, etc.

Weather-resistant molded bodies made of resins with poor weather resistance such as vinyl chloride resins, ABS resins, and polycarbonate resins, or various molded bodies coated with these resins such as PVC steel plates, or the surfaces of PVC wallpapers, etc. An attempt was made to improve their weather resistance by coating them with an acrylic resin composition that has excellent chemical resistance and stain resistance. 2. Many attempts have been made to improve stain resistance.

However, it also satisfies the above-mentioned flexibility, toughness, processability, 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 addition, especially for nosing interior materials such as wallpaper, or nosing equipment such as home appliances, a matte surface is generally preferred, but the above-mentioned acrylic resin composition originally has a high gloss. It is difficult to meet such demands because it is a synthetic resin.

That is, for example, it is difficult to obtain a sufficiently matte state by surface finishing using a calendar roll, which is generally performed in the production of the above-mentioned PVC wallpaper. On the other hand, a method of coating an acrylic resin composition by mixing it with a matting agent, most commonly an inorganic substance such as calcium carbonate or silica, is as follows:
By mixing this matting agent, the properties of the acrylic resin composition such as flexibility and toughness and its processability are significantly reduced.
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 proposed the above-mentioned flexibility.

As a result of intensive studies to obtain an acrylic resin composition suitable for use as a coating material or coating film material that has processability, stain resistance, weather resistance, and matte properties, we have developed an acrylic crosslinked elastic material, which will be described in detail later. A resin that is a blend of an acrylic multilayer structure with a fluoropolymer as its core, and a moderately crosslinked polymer matting agent whose main components are an aromatic vinyl monomer and hyalkyl (meth)acrylate. The present invention was achieved by discovering that a composition satisfies this objective.

That is, the present invention uses 1 to 99 parts by weight (hereinafter abbreviated as "parts") of a multilayer structure polymer (■) having the structure shown below, and the general formula CF2=CXY (wherein X and Y are H, F, and C7°). CF) or CH2=C-COOR (wherein R is) CH.

(representing a loloalkyl group) or a copolymer consisting of two or more of these monomers, or a ratio of these monomers is 50 parts by weight or more (hereinafter abbreviated as parts) At least one fluoropolymer (II) selected from the group consisting of copolymers with other copolymer monomers such as
) 1 to 99 parts of a polymer matting agent having the structure shown below (■) 1 to 7
This is a matte plastic resin composition containing 0 parts.

[Acrylic multilayer structure polymer (■)]

60 to 100 parts of alkyl acrylate having an alkyl group having 8 or less carbon atoms (AI), 0 to 40 parts of a monomer (A2) having a copolymerizable double bond, 0 to 1 part of Polyfunctional monomer (A3), above (AI)
``~ (As) o The composition of the grafting agent is 0.1 to 5 parts based on 100 parts of the total amount, the glue content is 60 parts or more, the swelling degree is 15 or less, and in the polymer (1) The innermost layer polymer (A) accounts for 5 to 80 parts, 51 to 100 parts of alkyl methacrylate (Bl) having an alkyl group having 4 or less carbon atoms, and 0 to 49 parts of copolymerizable double bonds. A monomer (B2) having a glass transition temperature (T2) of at least 6
at 0°C, and the amount occupied in the polymer (1) is 10
~85% of the outermost layer polymer (B) as a basic structural unit, and between the polymer (A) layer and the polymer (B) layer, an alkyl group having 10 to 90 parts of an alkyl group having 4 or less carbon atoms. Methacrylate (c+), 10-90 parts carbon number 8
Alkyl acrylate having the following alkyl group) (C
2), 0 to 20 parts of a monomer having a copolymerizable double bond (C3), 0 to 10 parts of a polyfunctional monomer (C4), the above (C1) to
An acrylic multilayer structure polymer ('I) capable of having at least one intermediate layer (C) consisting of 0.1 to 5 parts of a grafting agent based on 100 parts of the total amount of (C4).

[Polymer matting agent (■)]

10 to 100 parts of an 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 of an aromatic vinyl monomer; 40 parts of other monoethylenically unsaturated monomers, and the non-crosslinking monomer 1
A polymer matting agent (Ll) having an average particle diameter of 1 to 500 μm obtained by polymerizing 5 to 5 parts per 100 parts of a crosslinkable monomer having two or more double bonds in the molecule.

In the present invention, the acrylic multilayer structure polymer (
D is the innermost layer polymer (A) with lO ~ 70, and 5 ~ 40
The middle layer polymer (C) of Section 1 and the outer layer polymer (B) of Section 10~85, and the ratio of alkyl acrylate in each layer is from the innermost layer polymer (A) to the outermost layer polymer. It is most preferable if the direction is monotonically decreasing.

The present invention will be described in detail below, but first, the acrylic multilayer structure polymer (1) used in the present invention will be explained in more detail.

The innermost layer polymer (A) constituting the acrylic multilayer structure polymer (I) imparts flexibility and toughness to the polymer (I). The alkyl acrylate σ 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. -100 parts. The lower the glass transition temperature (T) of the homopolymer is, the more advantageous it is.

Examples of the monomer (A2) having a copolymerizable double bond include those copolymerizable with the above-mentioned alkyl acrylate (Al), such as lower alkyl methacrylate, lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, (Meth)acrylic acid derivatives such as methacrylic acid are preferred, and styrene, alkyl-substituted styrene, acrylonitrile, methacrylatrile and the like are also used in an amount of 0 to 40 parts.

The polyfunctional monomer () is used in a range of 0 to 10 parts,
Specifically, ethylene glycol dimethacrylate and propylene glycol dimethacrylate.

1.3-butylene glycol dimethacrylate l 11
4-butylene glycol dimethacrylate etc. are preferable L
Further examples include divinylbenzene, alkylene glycol diacrylate, and the like.

The total amount of the graft cross-agents (A1) to α,) is 100
specific examples include copolymerizable α,β-unsaturated monocarboxylic acid or dicarboxylic acid allyl ester, metaallyl Examples include ester, crotyl ester, triallyl cyanurate, triallyl isosif 5<L/-), and the like. Allyl esters include acrylic acid, methacrylic acid, and maleic acid.

Examples include allyl esters such as 7-maric acid and itaconic acid, with allyl methacrylate showing particularly excellent effects. If the amount of graft cross-agent used is less than 0.1 part, the effective amount of graft bonding will be too small, so layer destruction will easily occur during molding of the final polymer, resulting in a significant decrease in transparency, etc. I end up. In addition, if the content exceeds 5 parts, the elasticity is particularly low and the flexibility is reduced.

It cannot provide sufficient toughness.

The innermost layer polymer (A) is an acrylic multilayer structure polymer (
1) The amount occupied is 5 to 80%, preferably 10 to 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 (1). Moreover, if the amount exceeds 80%, the acrylic multilayer structure polymer (1) itself becomes rubbery and difficult to handle, and 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, in addition to the above, the innermost layer polymer (A) has a glu content,
Swelling degree 2 There are also preferable ranges for particle diameter, etc. In particular, regarding dull content and swelling degree, the dull content determined by the following measurement method is 60% or more, preferably B0chi or more, the swelling degree is 15 or less, It is preferably in the range of 3 to 15.

(Method for measuring glue content and degree of swelling) According to JIS K-6388, a predetermined amount of the polymer was sampled and immersed in methyl ethyl ketone (hereinafter abbreviated as MEK) for 48 hours to increase the degree of swelling, and the attached MEK was measured. After wiping it off, measure its weight, then dry and remove the MEK in a vacuum dryer, and calculate the absolute dry weight that has reached a constant weight using the following equation.

The particle size of the innermost layer polymer (A) is 500 to 500
If it is in the 0X range, the transparency and stress whitening resistance of the final multilayer structure polymer (D) will not be significantly reduced.

Next, as the alkyl methacrylate (Bl) having an alkyl group having 4 or less carbon atoms forming the outermost layer polymer (B) constituting the acrylic multilayer structure polymer (1), methyl methacrylate, ethyl methacrylate, propyl At least one of methacrylate and butyl methacrylate is used in an amount of 51 to 100 parts, with 2<tyl methacrylate being particularly preferred.

Examples of the monomer (B2) having a copolymerizable double bond include alkyl acrylates having an alkyl group having 8 or less carbon atoms, as well as those shown in the component (A2) above. These (B2) components are used in a range of 0 to 49 parts. The outermost layer polymer (B) is essentially a resin layer, and its T1 is 6.
It is necessary that the temperature is 0°C or higher.

Acrylic multilayer structure polymer (1) as outermost layer polymer (B)
The amount occupied in it is 10 to 85%, preferably 20 to 70%.
It is. If the amount is less than 10%, a stable polymer cannot be obtained from the viewpoint of polymerization, coagulation operations, etc. Moreover, if the amount exceeds 85%, the desired elasticity with a small content of the innermost layer polymer (A) cannot be obtained.

Incidentally, during the polymerization of the outermost layer polymer (B), it is possible, and often preferable, to adjust the degree of polymerization using a chain transfer agent or the like.

The acrylic multilayer structure polymer (1) used in the present invention has the above-mentioned innermost layer polymer (A) and outermost layer polymer (B) as basic structural units. In order to increase the affinity between the polymer (A) and the polymer (B) layer,
) layer and the polymer (B) layer having 10 to 90 parts of an alkyl group having 4 or less carbon atoms (alkyl methacrylate) (CI
), 90-10 parts of alkyl acrylate (C2) having an alkyl group having 8 or less carbon atoms, 0-20 parts of a monomer (C8) having a copolymerizable double bond, 0-10 parts of polyfunctional The ratio of alkyl acrylate in each layer is an intermediate layer (C) consisting of a grafting agent of 0.1 to 5 parts per 100 parts of the total amount of these (C1) to (C2). It is possible that at least one layer is arranged in a monotonically decreasing manner from layer (A) to layer (B), and it is more preferable to have a three-layer structure including one such intermediate layer. . Here, the components (C1) to (C4) and the grafting agent are the polymers (A) and (B).
) are used.

It is essential to use the above-mentioned grafting agent in this intermediate layer (C), and if it is not used, the multilayer structure polymer will easily whiten when subjected to stress, and the desired physical properties will be maintained. You can't get anything.

A particularly preferable amount of the grafting agent used is the intermediate layer (C).
0.5 to 100 parts of the total amount of other monomers constituting the
This is part 2.

The amount of this intermediate layer (C) in the acrylic multilayer structure polymer (I) is 70% or less, preferably 5 to 40%, and if it exceeds 70%, it is not preferable because it will upset the balance of the entire final polymer. .

Next, it is necessary that the outermost layer polymer (B) and the middle layer polymer (C) are grafted to the innermost layer polymer (A) to some extent, and the grafting ratio value is based on the following measurement method. is 2
5Lf6 or more is preferred.

(Method for measuring graft ratio) Weigh 0.59 of a sample into a 100 ml Erlenmeyer flask and measure
After adding K50d 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.

The above-mentioned acrylic multilayer structure polymer (1) can be easily obtained by a sequential multistage polymerization method using a conventional emulsion polymerization method. That is, the innermost layer polymer (A) is first obtained by emulsion polymerization, 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 was combed to obtain the multilayer structure polymer (1
) to complete the polymerization. Emulsifiers and catalysts used during this polymerization.

Coagulants and the like are not particularly regulated.

Note that an emulsion suspension polymerization method in which only the reed outer layer polymer (B) is converted into suspension polymerization after emulsion polymerization is also an advantageous method.

Next, the fluoropolymer (1) used in the present invention has the general formula CF, = CXY (in the formula, x, y,
, F.

C1, CF, or CH2=C-C0OR(
A homopolymer of the monomer represented by the formula (RH3 represents a fluoroalkyl group), or a copolymer consisting of two or more of these monomers, or a ratio of these monomers of 50 or more. It is at least one kind of polymer selected from the group consisting of copolymers with other copolymerizable monomers, and specifically, polybiylidene fluoride.

Polytetrafluoroethylene, polytetrafluorochloride ethylene, copolymer of tetrafluoroethylene and vinylidene fluoride, copolymer of tetrafluoroethylene and hexafluoropropylene, chili 2,2.2) Typical examples include lyfluoroethyl methacrylate.

Among these, polyvinylidene fluoride and a copolymer of tetrafluoroethylene and vinylidene fluoride are particularly preferred.

The above acrylic multilayer structure polymer (I) and the fluoropolymer (
The blending ratio with II) is 1/2 depending on the required properties.
It can be selected arbitrarily within the range of 99 to 99/l, but a ratio of acrylic multilayer structure polymer (1) of 51 or more improves the adhesion to the base material when used as a coating material. Preferable from this point of view.

Furthermore, the matting agent (III) used in the present invention does not just have to have a matting effect, but also has weather resistance,
It does not impair the characteristics of the blend composition of the above-mentioned acrylic multilayer structure polymer (1) and fluorine-based polymer (■), which serve as the base polymer, especially in terms of stain resistance, flexibility, toughness, and processing properties. It shouldn't be.

As a matting agent (III) that satisfies these conditions, 1
0 to 100 parts of alkyl methacrylate with an alkyl group having 1 to 4 carbon atoms, 0 to 60 parts of an alkyl group having 1 carbon number
-13 alkyl acrylate, 0 to 90 parts of an aromatic vinyl monomer, and 0 to 40 parts of other monoethylenically unsaturated monomers per 100 parts of the non-crosslinkable monomer. It is a polymeric matting agent (III) with an average particle diameter of 1 to 500 μ obtained by polymerizing 0.5 to 5 parts of a crosslinking monomer having two or more double bonds in the molecule. is necessary.

In this matting agent (III), the amount of crosslinking monomer added is particularly important, and specifically, the amount of non-crosslinking monomer 10
It is used in the range of 90.5 to 5 parts per 0 parts, but 1.5 to 5 parts.
A range of 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 if it is used in excess of 5 parts, the crosslinking will be too much and the resin will not form. Both are unsuitable because they reduce the compatibility of the polymer and the processability and physical properties of the matrix polymer.

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. It is particularly preferred from the viewpoint of controlling the degree of crosslinking. Typical examples of crosslinking monomers containing this stiff allyl group include allyl methacrylate, triallyl cyanurate, and triallyl cyanurate.

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 ([1)] is 10 to 100 parts, preferably 10 to 95 parts.
0 to 60 parts, preferably 3 to 40 parts of an alkyl acrylate having an alkyl group having 1 to 4 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. The alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms is typically methyl methacrylate, but ethyl methacrylate and butyl methacrylate can also be used. Typical examples of the alkyl acrylate having an alkyl group having 1 to 13 carbon atoms include ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Furthermore, styrene is a typical aromatic vinyl monomer,
Vinyltoluene, α-methylstyrene, 10-glycanized styrene, etc. can also be used.

Other monoethylenically unsaturated monomers include fumaric acid, maleic acid, copolymerizable carboxylic acids and their esters, and (meth)acrylic acid.

Vinyl halogenides, vinyl esters, acrylonitrile, etc. are used.

In addition, the particle size of the matting agent (III) used in the present invention is also a major constituent factor, and the particle size is usually 1.
~500μ is used, but 40~200μ is particularly preferred. If the particle size is less than 1 part, a sufficient matting effect cannot be obtained, whereas if the particle size exceeds 500μ, the film formability of the base material will be significantly reduced, and only a film with an extremely rough surface will be obtained. It's rare.

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, polymerization recipe examples can be used. There are no restrictions.

The amount of the matting agent (In) added is 1 to 70 parts, but usually 20 parts to 100 parts of the blend composition of the multilayer polymer (1) and the fluoropolymer (I[). In many cases, the effect is sufficient even if the amount is less than 100 yen.

and these acrylic multilayer structure polymers (I).

The fluoropolymer (If) and the matting agent (III) can be mixed by a normal mixing method such as using a Henschel mixer. ) It is preferable to heat the three to a temperature higher than the softening point of both and then mechanically mix them in that state, such as by passing the mixture through a screw type extruder where the mixture is simultaneously sheared and compressed, or by passing it between heated rolls. Any suitable mixing method is generally used, such as mixing in a heated high shear mixing device, such as a Burberry type mixer.

Furthermore, it is possible to add other usual additives such as antioxidants, ultraviolet absorber fillers, pigments, etc. to the resin composition of the present invention, if necessary, without significantly reducing the physical properties. It is also possible to appropriately blend other polymers within a range that does not cause the above.

The resin composition of the present invention thus obtained 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 can be directly extruded and coated onto a substrate. Furthermore, these films can be easily printed, and their design effects can be significantly improved.

EXAMPLES The present invention will be specifically explained below 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 l, 3-butylene dimethacrylate) BD acrylic tacrylate AMA cumene hydroperoxide CHPn-octyl mercaptan n-08
H lauroylnoya-oxide LPO methyl ethyl ketone MEK di-n-octyl phthalate DOP azobisisobutyl nitrile AIBN
Polyvinyl alcohol PVA Example 1 (1) In a reaction vessel with a cooler, 250 parts of ion-exchanged water,
1 part sulfosuccinic acid ester soda salt.

Sodium formaldehyde sulfoxylate 0.05
After stirring under nitrogen flow, 29 parts of BuA,
Charge a monomer mixture consisting of 1 part BD and 0.15 part AMA. In the above BuA, 0.1 g of CHP is dissolved in advance based on the total amount of BuA and BD. For all monomers added in subsequent steps, unless otherwise specified, one amount of CHP is included for each monomer. The reaction vessel was placed under a nitrogen gas flow at 20 Orp.
The temperature was raised to 50° C. while stirring at a rotational speed of m, and the temperature was 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°C and 10 parts of MMA was added.
, 10 parts of BuA, and 0.1 part of AMA are added over a period of 40 minutes and held for an additional 40 minutes to complete the polymerization of the intermediate layer (C). Finally 47.5
parts MMA, 2.5 parts BuA and 0.1 parts n=08
Adding the outermost layer polymer component consisting of H over 60 minutes and holding for an additional 60 minutes to complete polymerization of the outermost layer (B),
Acrylic multilayer structure polymer consisting of three layers (I-(a))
was manufactured.

The innermost layer polymer (A) of this acrylic multilayer structure polymer (I-(a)) has a glue content of 89, a swelling degree of 5.5, a particle size of about 1500 The content was 65%.

The latex of this acrylic multilayer structure polymer (Ila) was salted out using 5 parts of calcium chloride, filtered, washed with water, and dried to obtain a dry powder.

(2) Production of matting agent (In) The following compound is charged into a reaction vessel similar to that used in (1).

St 60 part MMA 2Q ttBuA
20〃 AMA 3tt n-O8HO, 1/1 AIBN 21/ tertiary calcium phosphate 2〃Water
200 After sufficiently purging the inside of the container with nitrogen gas, the mixture of the above compounds is heated to 75° C. while stirring, and polymerization is proceeded in nitrogen gas. 85 after 3 hours
The temperature was raised to 0.degree. C. and held for 3 hours, and then the temperature was 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 m-(a)). The weight average particle diameter of the obtained beads was about 70 μ, the degree of swelling in MEK was 12, and the gel content was 65 μ.

(3) Go part of the acrylic multilayer structure polymer (I-(a)) produced in (1) above, 20 parts of polyvinylidene fluoride (Kynar 901, NWOLTH Co., Ltd.), and the polymer produced in (2) above. 10 parts of a matting agent and 1 part of an ultraviolet absorber were blended using a Henschel mixer, and then shaped into pellets using an extruder equipped with a 40 mm diameter screw. After thoroughly drying this pellet, it was blown to a thickness of 80 mm using the inflation method.
A film of μ was formed. The tensile strength of this film is 3
10 K9/all, tensile elongation at break is 140%,
The 60 degree specular gloss was 25.

This film was attached to a galvanized sail 5 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. Demonstrated weather resistance.

Reference Example 1 Acrylic multilayer structure polymer (I-(a)) 80 parts.

By blending only 20 parts of polyvinyl fluoride and 1 part of an ultraviolet absorber, the above matting agent (III-(a))
A film obtained in the same manner as in Example 1 without blending had a tensile strength of g 320 K4/l:rA
Although the film showed good physical properties with a tensile elongation at break of 165%, the 60 degree specular gloss was as high as 120, and the resin composition did not have the matte properties that are the object of 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 (I[i-(a)).

The resulting film had a rough appearance and was insufficiently matte (60 degree specular gloss of 65), and was brittle (tensile elongation at break of 2).
5.) It was something.

Reference example 2 Acrylic multilayer structure polymer (I-(a)) i00 parts.

Only 1 part of the polymer matting agent (III-(a)) and 1 part of the ultraviolet absorber are blended, and the fluoropolymer (II-(a))
) was not blended, but the film obtained in the same manner as in Example 1 had a relatively good appearance and a sufficient matting effect (60 degree specular gloss of 28), but the tensile strength was 2.
The physical properties of the film were extremely poor, with a tensile elongation at break of 75 inches and a tensile strength of 60 K9/d.

Comparative Example 2 Innermost layer (A) and intermediate layer (
A film with a thickness of about 80 μm was formed by the same procedure as in Example 1, except that no graft cross-agent was used during the polymerization of C). The obtained film had a poor appearance and a tensile elongation value of 60.
% was low. Furthermore, this film easily whitens upon impact, and even in an accelerated exposure test using a sunshine weatherometer, the film showed yellowing and a significant decrease in tensile elongation. A matte resin composition was not obtained.

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, the reaction mixture was heated to 85% while stirring.
℃ for 2 hours, and then heat-treated at 95℃ for 30 minutes to complete the polymerization.After cooling, dehydration and drying were performed to obtain a matting agent (I[
l) -(b) was obtained.

MMA 60 parts BuA 35 〃 St 5 〃 AMA 2 tt n-O3HO,2// LPO2" PVA 2 tt Water 200 〃 The average particle diameter of the obtained matting agent ([1) - (b) is about 80 μ, contains dull The amount was 75% and the degree of swelling was 10.

A film was prepared in the same manner as in Example 1, except that 10 parts of the matting agent (III-(a)) and each part of the matting agent (Ill-(b)) were used as shown in Table 1 below. The values of the 60 degree mirror finish and tensile elongation were measured and the results are shown in Table 1.

Table 1 Example 3 Acrylic multilayer structure polymer produced in Example 1 (1-(
a)) 90 parts, copolymer of vinylidene fluoride and tetrafluoroethylene (Kycalf 201.-?Nwort) 1
0 parts, the polymeric matting agent produced in Example 1 (m - (a
)) 10 parts and 1 part of the ultraviolet absorber were blended using a Henschel mixer, and then shaped into pellets using an extruder equipped with a 40mm screw. After thoroughly drying the pellets, the same extruder was used to process the pellets using the T-Guy method to a thickness of 5 mm.
A film of 0 μm was formed.

The tensile strength of the film was 305 K9/cnl, the tensile elongation at break was 160%, and the 60 degree specular gloss was 28.

Apply this matte film to commercially available PVC wallpaper with a linear pressure of approximately 10
It was heated and pressed by passing it between two rolls heated to 120° C./cm. The weather resistance of the resulting wallpaper was evaluated using an accelerated exposure test using a fade meter in comparison with conventional wallpaper that is not laminated with a matte film.

Commercially available PVC wallpaper not laminated with a matte film 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 m of ion-exchanged water and 1 ml of sulfoconomonophosphate ester salt were added.
．． 5 parts, formaldehyde sulfoxylate)
After charging 0.05 parts and stirring under nitrogen flow, 58 parts of BuA, 2 parts of BD, 0.3 parts of AMA and B
A monomer mixture consisting of 0.1% CHP based on the total amount of uA and BD is charged.

The temperature of the reaction vessel was raised to 50°C while stirring under a nitrogen stream.
This state is maintained for 180 minutes to complete polymerization of the innermost layer polymer (A). The innermost layer polymer (A) has a dull content of 91%, a swelling degree of 563, and a particle size of about 1300.
It was X.

Next, the reaction system was heated to 75°C, 5 parts of HMA, 5 parts of B
uA, 3 parts of a monomer mixture consisting of 0.05 parts of AMA and 6 parts of CHP for the total amount of MMA and BuA.
27 parts of MMA,
A monomer mixture consisting of 3 parts of BuA and their 0.1% CHP was added over 60 minutes and a further 60
The outermost layer (B) was polymerized while maintaining that state for a minute, thereby completing the polymerization of an acrylic multilayer structure polymer (1-(b)) consisting of three layers. This acrylic multilayer structure polymer (1-(
The dal content of b)) 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) Blending 80 parts of the acrylic multilayer structure polymer (1-(b)) produced in (1) above with 20 parts of polyvinylidene fluoride, 10 parts of a polymer matting agent, and 1.5 parts of an ultraviolet absorber. Then, pellets were obtained in the same manner as in Example 1.

Using these pellets, semi-rigid vinyl chloride resin (DOP)
A laminated film was obtained by coextrusion with 20 parts of polyvinyl chloride (100μ of vinyl chloride, 100μ of acrylic).

The 60 degree specular gloss on the PVC side of the obtained laminated film was 9.
However, the resin composition of the present invention had a sufficiently low value of 31, indicating a uniformly matte state.

When this laminated film was subjected to an accelerated exposure test using a Zanshine Weatherometer, the sample with the PVC side exposed completely discolored and lost its luster after 500 hours, but the resin composition of the present invention On the side, no discoloration or fading was observed even after 3000 hours, and no migration of the plasticizer to the film surface was observed.

Claims (3)

[Claims] (1) Multilayer structure polymer (I) 1 having the structure shown below
~99 parts by weight and the general formula CF2=CXY (in the formula, X and Y represent H, F, CL, CF) or CH2=C-
A homopolymer of a monomer having C0OR (in the formula, R represents a fluoroalkyl group CH3) or a copolymer consisting of two or more of these monomers, or a ratio of these monomers in a weight ratio of 50 or more. 100 parts by weight of a thermoplastic resin composition comprising 1 to 99 parts by weight of at least one fluoropolymer (n) selected from the group consisting of copolymers with other copolymer monomers. In contrast, a matting thermoplastic resin composition containing 1 to 70 parts by weight of a polymer matting agent (■) having the structure shown below. [Acrylic multilayer structure polymer (I)] 660 to 100 parts by weight of alkyl acrylate (AI) having an alkyl group having 8 or less carbon atoms, 0 to 40 parts by weight of a monomer having a copolymerizable double bond ( A2), 0 to 10 parts by weight of polyfunctional monomer (A3), the above (A,
) to (A,) in a composition of 0.1 to 5 parts by weight of a grafting agent based on the total amount of 100 parts by weight, and the dull content is 60 weight percent or more and the swelling degree is 15 or less, and the polymer ( I
) the innermost layer polymer (
From the composition of A), 51 to 100 parts by weight of an alkyl methacrylate (B8) having an alkyl group having 4 or less carbon atoms, and 0 to 49 parts by weight of a monomer having a copolymerizable double bond (B2) The outermost layer polymer (B) has a glass transition temperature of at least 60° C. and accounts for 10 to 85% by weight in the polymer (I) as a basic structural unit,
Between the polymer (A) layer and the polymer (B) layer, 10 to 90 parts by weight of an alkyl methacrylate (C3) having an alkyl group having 4 or less carbon atoms, and 10 to 90 parts by weight of an alkyl group having 8 or less carbon atoms. Alkyl acrylate with
) (C2), 0 to 20 parts by weight of a copolymerizable monomer having a double bond (C3), 0 to 10 parts by weight of a polyfunctional monomer (C4), the above (C1
) to (C4) in an amount of 0.5 to 5 parts by weight based on the total amount of grafting agent (C)
1). [Polymer matting agent (■)] 10 to 100 parts by weight of an 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 to 90 parts by weight of an aromatic vinyl monomer, 0 to 40 parts by weight of other monoethylenically unsaturated monomers, and a non-crosslinking monomer (7).
100 parts by weight! A polymer matting agent (I[
l). (2) Claims characterized in that the fluoropolymer (II) of item (1) above is essentially polyvinylidene heptadide or a copolymer of vinylidene fluoride and tetrafluoroethane. The matte thermoplastic resin composition described in item (1). (3) Acrylic multilayer structure polymer (I) of item (1) above
is 51 to 95% by weight, and the fluoropolymer (n) is 5 to 49% by weight.
Claims characterized in that they are ratios of important features (
1) The matte thermoplastic resin composition described in item 1).