JP2015105371A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a synthetic resin laminate excellent in shape stability and surface hardness in atmosphere of high temperature or high humidity used for transparent substrate material and protective material.SOLUTION: There is provided a resin composition containing total 100 pts.mass of a resin composition of (A) and (B) consisting of a resin having a vinyl monomer having a mass average molecular weight of 10,000 to 500,000 as a constitutional unit (A) of 50 to 10 mass% and a specific styrene-unsaturated dicarboxylic acid-based copolymer (B) of 50 to 90 mass% having a styrenic monomer unit (b1) of 40 to 70 mass%, an unsaturated dicarboxylic acid monomer unit (b2) of 10 to 30 mass% and a vinyl monomer unit (b3) of 10 to 30 mass%, 0.001 to 1 pts.mass of phosphoric stabilizer and 0.01 to 0.5 pts.mass of a full ester compound of aliphatic alcohol and aliphatic carboxylic acid and a glass transition temperature of the resulting resin composition is 115°C or more and coefficient of water absorption of 1.0% or less.

Description

  The present invention relates to a resin composition containing a vinyl monomer. More specifically, it is a polymer blend of a specific styrene copolymer resin and a specific vinyl resin at a specific ratio, improves the heat distortion temperature and water absorption performance of the vinyl resin, and contains a vinyl monomer. It is a transparent resin composition characterized by maintaining the high pencil hardness of the resin to be used.

The advantages of methacrylic resin, represented by polymethyl methacrylate (hereinafter, PMMA), which is widely used as a transparent member and is also useful as a raw material for light and thermosetting resins, paints, adhesives, inks, etc., are transparency and weather resistance. It has excellent properties, has a good balance with mechanical properties, and has good workability. However, as a member of glazing material, display member (light guide plate / diffusion plate for liquid crystal display, screen plate for projection display, etc.), lighting cover, optical lens, etc. The demands are also diversified, and for example, improvements such as heat resistance and water absorption are required.
Conventionally known technologies for improving the heat resistance of PMMA include, for example, a copolymer resin of methyl methacrylate (hereinafter referred to as MMA) and α-methylstyrene (Patent Document 1), MMA and styrene, or α-methyl. Examples thereof include a copolymer resin with styrene and maleic anhydride (Patent Document 2), MMA, α-methylstyrene, and a copolymer resin with maleimide (Patent Document 3).
According to the methods described in Patent Documents 1 to 3, the heat resistance can be improved in all cases, but the polymerization rate is remarkably slow and a long time is required for the polymerization.

U.S. Pat. No. 3,135,723 JP 58-87104 A JP 48-95490 A

  The present invention was devised in view of the above-mentioned problems. The glass transition temperature is high and further low while maintaining transparency without impairing the high surface hardness inherent to the resin containing the vinyl monomer. The present invention relates to a resin composition containing a vinyl monomer excellent in water absorption.

As a result of intensive studies to solve the above problems, the present inventors have obtained i) 45 to 70% by mass of a styrene monomer unit, 10 to 30% by mass of an unsaturated dicarboxylic anhydride monomer unit, Polymer containing 10 to 35% by weight of a specific styrene-unsaturated dicarboxylic acid copolymer of 50 to 90% by weight and ii) 50 to 10% by weight of a resin having a vinyl monomer as a constituent unit As a result of the alloying, it was found that a resin composition having a high transparency and heat resistance and a low water absorption can be obtained, and the present invention has been achieved.
That is, the present invention provides the following synthetic resin composition and a molded article using the resin composition.

<1> 50 to 10% by mass of a resin (A) having a vinyl monomer having a mass average molecular weight of 10,000 to 500,000 as a structural unit,
Styrene monomer unit (b1) 40-70% by mass, unsaturated dicarboxylic acid monomer unit (b2) 10-30% by mass, vinyl monomer unit (b3) 10-30% by mass 0.001 to 1 part by mass of a phosphorus stabilizer with respect to 100 parts by mass of the resin components (A) and (B) consisting of 50 to 90% by mass of the styrene-unsaturated dicarboxylic acid copolymer (B), It contains 0.01 to 0.5 parts by mass of a full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid, and the resulting resin composition has a glass transition temperature of 115 ° C. or higher and a saturated water absorption of 1.0% or lower. It is a resin composition characterized by being.
<2> The resin composition according to <1>, wherein the vinyl monomer units of the resin components (A) and (b3) are methyl methacrylate.
<3> The resin composition according to any one of <1> to <2>, wherein the styrenic monomer unit (b1) is styrene.
<4> The resin composition according to any one of <1> to <3>, wherein the unsaturated dicarboxylic acid monomer unit (b2) is maleic anhydride.
<5> A molded article comprising the resin composition according to any one of <1> to <4>.

  According to the present invention, a synthetic resin composition excellent in shape stability, surface hardness and / or heat resistance in a high temperature or high humidity environment is provided, and the synthetic resin composition includes a transparent substrate material and a transparent protective material. Used as a raw material. Specifically, it is suitable for portable display devices such as mobile phone terminals, portable electronic play equipment, portable information terminals, and mobile PCs, and stationary display devices such as notebook PCs, desktop PC liquid crystal monitors, and liquid crystal televisions. used.

  Hereinafter, the present invention will be described in detail with reference to production examples and examples, but the present invention is not limited to the illustrated production examples and examples, and the scope of the present invention is not greatly deviated. If so, it can be changed to any method.

  The present invention is a resin comprising 50 to 90% by mass of a specific styrene-unsaturated dicarboxylic acid copolymer (B) and 50 to 10% by mass of a resin (A) having a vinyl monomer as a structural unit. It relates to a composition. Hereinafter, the resin component (A) containing a vinyl monomer and the resin component (B) of a styrene-unsaturated dicarboxylic acid copolymer will be sequentially described.

<Resin containing vinyl monomer (A)>
Examples of the resin (A) containing a vinyl monomer used in the present invention include acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and methacrylic acid. , And vinyl monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate are homopolymerized, and methyl methacrylate is particularly preferred as the monomer unit. Further, a copolymer containing two or more kinds of the monomer units may be used.
The mass average molecular weight of the resin (A) is 10,000 to 500,000, preferably 50,000 to 300,000.

<Styrene-unsaturated dicarboxylic acid copolymer (B)>
The resin component (B) used in the resin composition of the present invention includes a styrene monomer unit (b1) and an unsaturated dicarboxylic acid anhydride monomer unit (b2), and is copolymerizable. A vinyl monomer (b3) is included.

<Styrene monomer>
The styrene monomer is not particularly limited, and any known styrene monomer can be used. From the viewpoint of availability, styrene, α-methylstyrene, o-methylstyrene, m- Examples include methyl styrene, p-methyl styrene, t-butyl styrene and the like. Among these, styrene is particularly preferable from the viewpoint of compatibility. Two or more of these styrenic monomers may be mixed.
<Unsaturated dicarboxylic acid anhydride monomer>
Examples of the unsaturated dicarboxylic anhydride monomer include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, and maleic anhydride is preferred from the viewpoint of compatibility with vinyl monomers. Two or more of these unsaturated dicarboxylic acid anhydride monomers may be mixed.
<Vinyl monomer>
Examples of vinyl monomers include acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, and n methacrylate. -Vinyl monomers such as butyl and 2-ethylhexyl methacrylate are listed. From the viewpoint of compatibility with vinyl monomers, methyl methacrylate (MMA) is preferred. Two or more of these vinyl monomers may be mixed.

<Composition ratio of styrene-unsaturated dicarboxylic acid copolymer>
The composition ratio of the styrene-unsaturated dicarboxylic acid copolymer is 40 to 70% by mass of the styrene monomer unit (b1), 10 to 30% by mass of the unsaturated dicarboxylic acid monomer unit (b2), It is 10-30 mass% of monomer units (b3).

  The weight average molecular weight of the styrene-unsaturated dicarboxylic acid copolymer (B) is preferably 50,000 to 200,000, more preferably 80,000 to 200,000. When the weight average molecular weight is 50,000 to 200,000, the compatibility with the resin component (A) containing a vinyl monomer is good, and the effect of improving heat resistance is excellent. The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the resin component (B) were measured using gel permeation chromatography using THF or chloroform as a solvent. It can be carried out.

  The resin composition of the present invention contains a phosphorus stabilizer. Phosphorus stabilizers are generally used for stability and resin molding at high temperatures when melt-kneading a resin (A) containing a vinyl monomer and a styrene-unsaturated dicarboxylic acid copolymer (B). It is effective for improving heat stability during body use.

  Examples of the phosphorus compound used in the present invention include phosphorous acid, phosphoric acid, phosphite ester, phosphate ester, etc. Among them, phosphite contains trivalent phosphorus and easily exhibits a discoloration suppressing effect. Phosphites such as phosphonite are preferred.

  Specific examples of the phosphite include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, and tris. (Tridecyl) phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra (tridecyl) pentaerythritol tetra Phosphite, hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-t rt-butylphenyldi (tridecyl) phosphite) tetra (tridecyl) 4,4'-isopropylidenediphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilauryl Pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite Polymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphos Aito, 2,2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like.

  Examples of phosphonites include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6- -Tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, and tetrakis (2,6-di-) tert-butylphenyl) -3,3′-biphenylenediphosphonite.

  Examples of the acid phosphate include methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, and lauryl phosphate. Phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonyl phenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid Sulfate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phenyl Acid phosphate, bisnonylphenyl acid phosphate, etc. are mentioned.

  Among the phosphites, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) penta Erythritol diphosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferable, and heat resistance is good. Tris (2,4-di-tert-butylphenyl) phosphite is particularly preferred in that it is difficult to hydrolyze.

  The content of the phosphorus stabilizer (C) used in the present invention is 100 parts by mass in total of the resin component (A) containing the vinyl monomer and the resin component of the styrene-unsaturated dicarboxylic acid copolymer (B). Is usually 0.001 part by mass or more, preferably 0.003 part by mass or more, more preferably 0.005 part by mass or more, and 1 part by mass or less, or 0.1 part by mass or less, preferably 0. It is 08 parts by mass or less, more preferably 0.06 parts by mass or less. If the content of the phosphorus stabilizer is less than or equal to the lower limit of the range, the thermal stability effect may be insufficient, and if the content of the phosphorus stabilizer exceeds the upper limit of the range, the effect May end up becoming uneconomical

<Full esterified product of aliphatic alcohol and aliphatic carboxylic acid>
The resin composition containing the vinyl monomer of the present invention can contain a full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid as desired. By containing a full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid, the releasability from the mold during molding can be further improved.

  Examples of the aliphatic carboxylic acid constituting the full esterified product include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid and tricarboxylic acid. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Of these, preferred aliphatic carboxylic acids are mono- or dicarboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferred. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melicic acid, tetratriacontanoic acid. , Montanic acid, glutaric acid, adipic acid, azelaic acid and the like.

  On the other hand, examples of the aliphatic alcohol component constituting the fully esterified product include saturated or unsaturated monohydric alcohols, saturated or unsaturated polyhydric alcohols, and the like. These alcohols may have a substituent such as a fluorine atom or an aryl group. Of these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the aliphatic alcohol also includes an alicyclic alcohol.

  Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc. These aliphatic carboxylic acid esters may contain an aliphatic carboxylic acid and / or alcohol as impurities, and may be a mixture of a plurality of compounds.

  In addition, the esterification rate of the full esterified product of the aliphatic alcohol and the aliphatic carboxylic acid is not necessarily 100%, and may be 80% or more. The esterification rate of the full esterified product according to the present invention is preferably 85% or more, particularly preferably 90% or more.

  Further, a full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid includes a full esterified product of a monoaliphatic alcohol and a monoaliphatic carboxylic acid, and a full esterified product of a polyaliphatic alcohol and a monoaliphatic carboxylic acid. It is preferable to contain.

  As a full esterified product of monoaliphatic alcohol and monoaliphatic carboxylic acid, a full esterified product of stearyl alcohol and stearic acid (stearyl stearate), a full esterified product of behenyl alcohol and behenic acid (behenyl behenate) is preferable. As a full esterified product of a polyaliphatic alcohol and a monoaliphatic carboxylic acid, a full esterified product of glycerol serine and stearic acid (glycerol tristearate), a full esterified product of pentaerythritol and stearic acid (pentaerythritol tetra) Stearylate) is preferred, and glycerin tristearate is particularly preferred.

  The content of the full esterified product (D) of an aliphatic alcohol and an aliphatic carboxylic acid is a resin component of a resin (A) containing a vinyl monomer and a styrene-unsaturated dicarboxylic acid copolymer (B). 1 part by mass or less, for example, 0.01 to 0.5 part by mass, preferably 0.4 part by mass or less with respect to 100 parts by mass in total. When it exceeds 1 part by mass, there are problems such as degradation of hydrolysis resistance and mold contamination during injection molding and extrusion molding.

<Antioxidant>
The resin composition of the present invention preferably contains an antioxidant as desired. By containing the antioxidant, it is possible to suppress hue deterioration and deterioration of mechanical properties during heat retention.

  Examples of the antioxidant include hindered phenol-based antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, ''-(Mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert- Butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5- Di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4 6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Specific examples of such phenolic antioxidants include “Irganox 1010”, “Irganox 1076” manufactured by Ciba, “Adekastab AO-50”, “Adekastab AO-60” manufactured by Adeka, and the like. Is mentioned.
In addition, 1 type may contain antioxidant and 2 or more types may contain it by arbitrary combinations and a ratio.

<Ultraviolet absorber>
The resin composition containing the vinyl monomer of the present invention preferably contains an ultraviolet absorber as desired. By containing the ultraviolet absorber, the weather resistance of the resin composition containing the vinyl monomer of the present invention can be improved.

  Examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; organics such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, hindered amine compounds, etc. Examples include ultraviolet absorbers. In these, an organic ultraviolet absorber is preferable and a benzotriazole compound is more preferable. By selecting the organic ultraviolet absorber, the transparency and mechanical properties of the resin composition containing the vinyl monomer of the present invention are improved.

  Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3 ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2 2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like, among others 2- (2'-hydroxy- 5′-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] are preferred. In particular, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is preferred. Specific examples of such a benzotriazole compound include “Seesorb 701”, “Seesorb 705”, “Seesorb 703”, “Seesorb 702”, “Seesorb 704”, and “Seesorb 709” manufactured by Sipro Kasei Co., Ltd. “Biosorb 520”, “Biosorb 582”, “Biosorb 580”, “Biosorb 583” manufactured by Yakuhin Kagaku Co., Ltd. “Chemisorb 71”, “Chemisorb 72” manufactured by Chemipro Kasei Co., Ltd. “Siasorb UV5411” manufactured by Cytec Industries, Inc. “ “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, “Tinuvin P”, “Tinubin 234”, “Tinubin 326” manufactured by Ciba Specialty Chemicals, “Tinuvin 327”, “Tinuvin 328”, and the like.

  Specific examples of the benzophenone compound include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxy Benzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4 4,4′-dimethoxybenzophenone and the like. Specific examples of such a benzophenone compound include “Seesorb 100”, “Seesorb 101”, “Seesorb 101S”, “Seesorb 102”, and “Seesorb 102” manufactured by Cypro Kasei Co., Ltd. Seesorb 103 ", joint medicine “Biosorb 100”, “Biosorb 110”, “Biosorb 130”, manufactured by Kemipro Kasei Co., Ltd. “Chemisorb 10”, “Chemisorb 11”, “Chemisorb 11S”, “Chemisorb 12”, “Chemsorb 13”, “Chemisorb 111” BASF “Ubinur 400”, BASF “Ubinur M-40”, BASF “Ubinur MS-40”, Cytec Industries “Thiasorb UV9”, “Thiasorb UV284”, “Thiasorb UV531”, “Thiasorb” UV24 "," ADEKA STAB 1413 "," ADEKA STAB LA-51 "manufactured by Adeka Corporation and the like.

  Specific examples of the salicylate compound include phenyl salicylate and 4-tert-butylphenyl salicylate. Specific examples of such a salicylate compound include, for example, “Seesorb 201” and “Seesorb” manufactured by Sipro Kasei Co., Ltd. 202 ”,“ Kemisorb 21 ”,“ Kemisorb 22 ”manufactured by Chemipro Kasei Co., Ltd., and the like.

  Specific examples of the cyanoacrylate compound include, for example, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like. Specifically, for example, “Seasorb 501” manufactured by Sipro Kasei Co., Ltd., “Biosorb 910” manufactured by Kyodo Yakuhin Co., Ltd., “Ubisolator 300” manufactured by Daiichi Kasei Co., Ltd., “Ubinur N-35”, “Ubinur N-N-” manufactured by BASF Corporation. 539 "and the like.

  Specific examples of the oxanilide compound include, for example, 2-ethoxy-2′-ethyl oxalinic acid bis-arinide and the like. Specific examples of such an oxalinide compound include “Sanduboa” manufactured by Clariant Corporation. VSU "etc. are mentioned.

  As the malonic acid ester compound, 2- (alkylidene) malonic acid esters are preferable, and 2- (1-arylalkylidene) malonic acid esters are more preferable. Specific examples of such a malonic ester compound include “PR-25” manufactured by Clariant Japan, “B-CAP” manufactured by Ciba Specialty Chemicals, and the like.

  The content of the ultraviolet absorber is usually 0 with respect to a total of 100 parts by mass of the resin component (A) having a vinyl monomer as a structural unit and the resin component of the styrene-unsaturated dicarboxylic acid copolymer (B). 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and usually 3 parts by mass or less, preferably 2 parts by mass or less, more preferably 1 part by mass or less. is there. If the content of the UV absorber is below the lower limit of the above range, the effect of improving the weather resistance may be insufficient, and if the content of the UV absorber exceeds the upper limit of the above range, the mold Debogit etc. may occur and cause mold contamination. In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

  In the present invention, the method for producing a resin composition containing a vinyl monomer is not particularly limited, and necessary components are mixed in advance using a mixer such as a tumbler, a Henschel mixer, or a super mixer. A known method such as melt kneading by a machine such as a Banbury mixer, a roll, a Brabender, a single screw extruder, a twin screw extruder, or a pressure kneader can be applied.

  The resin composition in the present invention is preferably filtered and purified by filtering. By producing or laminating through a filter, a synthetic resin laminate having few appearance defects such as foreign matters and defects can be obtained. There is no restriction | limiting in particular in the filtration method, Melt filtration, solution filtration, or those combinations can be used.

  There is no restriction | limiting in particular in the filter to be used, A well-known thing can be used and it selects suitably by the use temperature of each material, a viscosity, and filtration precision. The filter medium is not particularly limited, but polypropylene, cotton, polyester, viscose rayon and glass fiber nonwoven fabric or roving yarn roll, phenol resin impregnated cellulose, metal fiber nonwoven fabric sintered body, metal powder sintered body, breaker plate, Alternatively, any combination of these can be used. In view of heat resistance, durability, and pressure resistance, a type in which a metal fiber nonwoven fabric is sintered is preferable.

  The filtration accuracy is 50 μm or less, preferably 30 μm or less, and more preferably 10 μm or less for the resin (A) containing a vinyl monomer and the styrene-unsaturated dicarboxylic acid copolymer (B). The filtration accuracy of the hard coat agent is 20 μm or less, preferably 10 μm or less, and more preferably 5 μm or less because it is applied to the outermost layer of the synthetic resin laminate.

  For filtration of the resin (A) styrene-unsaturated dicarboxylic acid copolymer containing a vinyl monomer, it is preferable to use, for example, a polymer filter used for thermoplastic resin melt filtration. The polymer filter is classified into a leaf disk filter, a candle filter, a pack disk filter, a cylindrical filter and the like depending on its structure, and a leaf disk filter having a large effective filtration area is particularly suitable.

  The glass transition temperature of the resin composition of the present invention is 115 ° C. or higher, preferably 118 ° C. or higher. Further, the saturated water absorption of the resin composition of the present invention is 1.0% or less, preferably 0.8% or less.

Hereinafter, the present invention will be described specifically by way of examples. However, this invention is not restrict | limited at all by these Examples.
Measurement of physical properties of the resins obtained in the production examples and evaluation of the resin compositions obtained in the examples and comparative examples were performed as follows.

<Weight average molecular weight>
Based on a calibration curve obtained by previously dissolving standard polystyrene in chloroform and measured by gel permeation chromatography (GPC), a resin (A) containing a vinyl monomer and a styrene-unsaturated dicarboxylic acid copolymer (B ) Was similarly measured by GPC. The weight average molecular weight of each was calculated by comparing the two. The apparatus configuration of GPC is as follows.
Device: Weights 2690
Column: Shodex GPC KF-805L 8φ × 300 mm 2-linked developing solvent: chloroform flow rate: 1 ml / min
Temperature: 30 ° C
Detector: UV ... 486 nm Styrene-unsaturated dicarboxylic acid copolymer (B)
RI: Resin containing vinyl monomer (A)

<Water absorption rate>
The water absorption rate was measured according to JIS-K7209 A method. First, a test piece of 60 mm × 60 mm × 1.0 mm prepared by press molding was prepared, and it was dried in an oven at 50 ° C. After 24 hours, the test piece was taken out of the oven and cooled in a desiccator adjusted to 23 ° C. After 1 hour, the weight of the test piece was measured and then put into water at 23 ° C. After 300 hours, the test piece was taken out of the water, the surface moisture was wiped off, and the weight was measured. The water absorption was calculated by dividing the difference between the weight immediately after drying in water and the weight immediately after drying by the weight immediately after drying, and multiplying that value by 100. A water absorption rate of 1.0% or less was accepted.

<Pencil scratch hardness test>
In accordance with JIS K 5600-5-4, the hardness of the hardest pencil that did not cause scars was gradually increased by increasing the hardness against the surface of the resin (A) at an angle of 45 degrees with respect to the surface and a load of 750 g. The hardness was evaluated. A pencil hardness of H or higher was accepted.

<Glass transition temperature test>
In a DSC curve obtained by using a differential scanning calorimeter Pyris 1 manufactured by Perkin Elmer, measured at a heating rate of 10 ° C./min after being held at 25 ° C. for 1 minute in a nitrogen atmosphere, and using a tangential method. The intersection of two tangents was determined as the glass transition temperature. A glass transition temperature of 115 ° C. or higher was considered acceptable.

<Examples of various materials>
Examples of the resin A and the styrene-unsaturated dicarboxylic acid copolymer B containing a vinyl monomer are shown below, but are not limited thereto.
A7: Styrene-unsaturated dicarboxylic acid copolymer: KX-378, Denki Kagaku Kogyo Co., Ltd.
A8: Styrene-unsaturated dicarboxylic acid copolymer: KX-381, Denki Kagaku Kogyo Co., Ltd.

Example 1 [resin composition (production of A1 pellets)]
Styrene-unsaturated dicarboxylic acid copolymer (B) as KX-378 (manufactured by Denki Kagaku Kogyo, glass transition temperature 126 ° C., weight average molecular weight: 170,000, b1: b2: b3 = 65: 15: 20) 50 A blend of 50% by weight of methyl methacrylate resin parapet HR-L (manufactured by Kuraray), 500 ppm of phosphorus additive PEP36 (manufactured by ADEKA) and 2000 ppm of stearic acid monoglyceride (product name: H-100, manufactured by Riken Vitamin) After mixing for 20 minutes, using a twin screw extruder with a screw diameter of 26 mm, the mixture was melt-kneaded at a cylinder temperature of 260 ° C., extruded into a strand, and pelletized with a pelletizer. The pellets could be manufactured stably. The obtained pellet was transparent, and the glass transition temperature was 118 ° C. The water absorption was 0.8% and the pencil hardness was H.

Example 2 [Production of resin composition (A2) pellets]
80% by mass of KX-378 (manufactured by Denki Kagaku Kogyo, weight average molecular weight: 170,000, b1: b2: b3 = 65: 15: 20) as styrene-unsaturated dicarboxylic acid copolymer (B), methyl methacrylate Charge 20% by mass of resin parapet HR-L (manufactured by Kuraray), 500 ppm of phosphorus additive PEP36 (manufactured by ADEKA) and 0.2% of stearic acid monoglyceride (product name: H-100, manufactured by Riken Vitamin), and blender for 20 minutes After mixing, the mixture was melt-kneaded at a cylinder temperature of 260 ° C. using a twin screw extruder with a screw diameter of 26 mm, extruded into a strand shape, and pelletized with a pelletizer. The pellets could be manufactured stably. The obtained pellet was transparent, the glass transition temperature was 123 ° C., the water absorption was 0.55%, and the pencil hardness was H.

Example 3 [Production of resin composition (A3) pellets]
65% by mass of KX-378 (manufactured by Denki Kagaku Kogyo, weight average molecular weight: 170,000, b1: b2: b3 = 65: 15: 20) as styrene-unsaturated dicarboxylic acid copolymer (B), methyl methacrylate Resin Parapet HR-L (manufactured by Kuraray) 35% by mass, phosphorus additive PEP36 (manufactured by ADEKA) 500 ppm and stearic acid monoglyceride (product name: H-100, manufactured by Riken Vitamin) 0.2% were charged and mixed in a blender for 20 minutes. Then, using a twin screw extruder with a screw diameter of 26 mm, the mixture was melt kneaded at a cylinder temperature of 260 ° C., extruded into a strand shape, and pelletized with a pelletizer. The pellets could be manufactured stably. The obtained pellet was transparent, the glass transition temperature was 120 ° C., the water absorption was 0.65%, and the pencil hardness was H.

Example 4 [Production of resin composition (A4) pellets]
50% by mass of KX-381 (manufactured by Denki Kagaku Kogyo Co., Ltd., weight average molecular weight: 185,000, b1: b2: b3 = 55: 20: 25) as styrene-unsaturated dicarboxylic acid copolymer (B), methyl methacrylate Resin Parapet HR-L (manufactured by Kuraray) 50 mass%, phosphorus additive PEP36 (manufactured by ADEKA) 500 ppm and stearic acid monoglyceride (product name: H-100, manufactured by Riken Vitamin) 0.2% were charged and mixed for 20 minutes with a blender. Then, using a twin screw extruder with a screw diameter of 26 mm, the mixture was melt kneaded at a cylinder temperature of 260 ° C., extruded into a strand shape, and pelletized with a pelletizer. The pellets could be manufactured stably. The obtained pellet was transparent, the glass transition temperature was 122 ° C., the water absorption was 0.9%, and the pencil hardness was H.

Example 5 [Production of resin composition (A5) pellets]
80% by mass of KX-381 (manufactured by Denki Kagaku Kogyo, weight average molecular weight: 185,000, b1: b2: b3 = 55: 20: 25) as styrene-unsaturated dicarboxylic acid copolymer (B), methyl methacrylate Charge 20% by mass of resin parapet HR-L (manufactured by Kuraray), 500 ppm of phosphorus additive PEP36 (manufactured by ADEKA) and 0.2% of stearic acid monoglyceride (product name: H-100, manufactured by Riken Vitamin), and blender for 20 minutes After mixing, the mixture was melt-kneaded at a cylinder temperature of 260 ° C. using a twin screw extruder with a screw diameter of 26 mm, extruded into a strand shape, and pelletized with a pelletizer. The pellets could be manufactured stably. The obtained pellet was transparent, the glass transition temperature was 129 ° C., the water absorption was 0.60%, and the pencil hardness was H.

Example 6 [Production of resin composition (A6) pellets]
65% by mass of KX-381 (manufactured by Denki Kagaku Kogyo, weight average molecular weight: 185,000, b1: b2: b3 = 55: 20: 25) as styrene-unsaturated dicarboxylic acid copolymer (B), methyl methacrylate Resin Parapet HR-L (manufactured by Kuraray) 35% by mass, phosphorus additive PEP36 (manufactured by ADEKA) 500 ppm and stearic acid monoglyceride (product name: H-100, manufactured by Riken Vitamin) 0.2% were charged and mixed in a blender for 20 minutes. Then, using a twin screw extruder with a screw diameter of 26 mm, the mixture was melt kneaded at a cylinder temperature of 260 ° C., extruded into a strand shape, and pelletized with a pelletizer. The pellets could be manufactured stably. The obtained pellets were transparent, the glass transition temperature was 124 ° C., the water absorption rate was 0.75%, and the pencil hardness was H.

Comparative Example 1 [Production of Resin (B1) Pellets]
Pelletization was performed in the same manner as in Example 1 using only the methyl methacrylate resin parapet HR-L (manufactured by Kuraray) as a material. The pellets could be manufactured stably. The obtained pellet was transparent, the glass transition temperature was 105 ° C., the water absorption was 2.1%, and the pencil hardness was 3H.

Comparative Example 2 [Production of Resin (B2) Pellets]
25% by mass of KX-378 (manufactured by Denki Kagaku Kogyo Co., Ltd., weight average molecular weight: 00000, b1: b2: b3 = 65: 15: 20) as a styrene-unsaturated dicarboxylic acid copolymer (B), and a methyl methacrylate resin parapet HR-L (manufactured by Kuraray) 75% by mass, mixed for 20 minutes with a blender, melt-kneaded using a twin screw extruder with a screw diameter of 26 mm at a cylinder temperature of 260 ° C., extruded into a strand, and pelletized with a pelletizer Turned into. The pellets could be manufactured stably.
The obtained pellet was transparent, the glass transition temperature was 113 ° C., the water absorption was 1.1%, and the pencil hardness was 2H.

  As is clear from the results of Examples and Comparative Examples, the resin composition of the present invention in which a resin (A) containing a vinyl monomer and a styrene-unsaturated dicarboxylic acid copolymer (B) are polymer-alloyed. Compared with the resin composition of the comparative example, the glass transition temperature is high while maintaining the transparency without impairing the high surface hardness inherent to the resin containing the vinyl monomer, and further the chemical resistance. It is a resin composition containing an excellent vinyl monomer. The synthetic resin composition of the present invention is characterized in that the water absorption is significantly improved while maintaining high surface hardness as compared with the resin (A) containing a vinyl monomer.

From Table 1, it is confirmed that the synthetic resin composition of the present invention is excellent in shape stability, surface hardness and heat resistance in a high temperature and high humidity environment.

  The synthetic resin composition of the present invention is characterized by excellent shape stability, surface hardness and heat resistance in high temperature and high humidity environments, and is suitably used as a transparent substrate material, a transparent protective material, and the like. In particular, it is suitably used as a display unit front plate or a surface layer resin for a touch panel substrate of OA equipment / portable electronic equipment.

Claims (5)

50 to 10% by mass of a resin (A) having a vinyl monomer having a mass average molecular weight of 10,000 to 500,000 as a structural unit,
Styrene monomer unit (b1) 40-70% by mass, unsaturated dicarboxylic acid monomer unit (b2) 10-30% by mass, vinyl monomer unit (b3) 10-30% by mass 0.001 to 1 part by mass of a phosphorus stabilizer with respect to 100 parts by mass of the resin components (A) and (B) consisting of 50 to 90% by mass of the styrene-unsaturated dicarboxylic acid copolymer (B), It contains 0.01 to 0.5 parts by mass of a full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid, and the resulting resin composition has a glass transition temperature of 115 ° C. or higher and a saturated water absorption of 1.0% or lower. A resin composition characterized by the above.   The resin composition according to claim 1, wherein the vinyl monomer units of the resin components (A) and (b3) are methyl methacrylate.   The resin composition according to claim 1, wherein the styrenic monomer unit (b1) is styrene.   The resin composition according to any one of claims 1 to 3, wherein the unsaturated dicarboxylic acid monomer unit (b2) is maleic anhydride.   The molded article containing the resin composition in any one of Claims 1-4.