JPS62275147A - Impact-resistant methacrylate resin composition - Google Patents

Abstract

PURPOSE:To provide the title resin compsn. having excellent impact resistance, consisting of a methacrylate resin and two specified rubber components. CONSTITUTION:A rubber component (A) obtd. by polymerizing 10-100pts. (by weight; the same applies hereinbelow) mixture (a) of 80-100% (by weight; the same applies hereinbelow) methyl methacrylate and other copolymerizable monomer in the presence of a copolymer (b) having a particle size of 0.05-0.15mu obtd. by polymerizing 100pts. monomer mixture (c) of 69.9-89.9wt% 2-8C alkyl acrylate, 30-10% styrene and 0.1-5% polymerizable polyfunctional monomer which is an ester derived from an acid component such as (meth)acrylic acid, etc. and an unsaturated alcohol component such as allyl alcohol, etc. is mixed with a rubber component (B) obtd. by polymerizing 10-1,000pts. component (a) in one portion or several portions in the presence of 100pts. two0layered rubbery material composed of the component (b) and a polymer having a particle size of 0.18-0.45mu, obtd. by polymerizing 90-40pts. component (c) in the presence of 1-60pts. polymer composed of not less than 40% methyl methacrylate unit or not less than 80% methyl methacrylate unit and/or 1-8C alkyl acrylate unit, in a weight ratio of A-B of 1/6-6/1. 90-10% resulting rubber component is blended with 10-90% methacrylate resin.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a methacrylic resin composition having excellent impact resistance, and more specifically relates to a methacrylic resin composition having a specific structure and particle size. A methacrylic resin composition having excellent transparency, surface gloss, and good impact resistance, obtained by blending a specific amount of a rubber fraction with a specific methacrylic resin whose main constituent unit is methyl methacrylate. .

[Conventional technology]

Among plastic materials, methacrylic resin has outstanding properties such as transparency, optical properties, surface gloss, surface hardness, and mechanical properties.It also has extremely excellent properties such as durability, weather resistance, and moldability. have. Taking advantage of these properties, they are used in a wide variety of fields, including lighting equipment, signboards, window materials, optical lenses, vehicle parts, and various displays.

However, methacrylic resin has the problem of insufficient impact resistance, and its improvement is strongly desired in individual application fields.

Techniques for imparting impact resistance to methacrylic resin without sacrificing all of its original properties have not been studied for a long time. The inventors also previously polymerized a monomer mixture in a specific composition range of an acrylic acid alkyl ester, an aromatic vinyl monomer, and an allyl (meth)acrylate in the presence of a specific amount of the first step. In the second step, a specific amount of methyl methacrylate is polymerized as the main component, and a specific amount of rubbery elastic material is obtained by graft copolymerizing the entire methyl methacrylate and a methacrylic resin containing methyl methacrylate as the main component. (Japanese Patent Publication No. 54-18298), and in this method, the main components are acrylic acid alkyl ester and aromatic vinyl monomer present inside the second step, which has methyl methacrylate as the main component. The first stage is a copolymer of a monomer mixture, and the rubber-like elastic body has a hard resin core containing methyl methacrylate as a main constituent unit and has three or more different structures. A methacrylic resin containing methyl methacrylate as the main constituent unit.

According to the former method described above, although it is possible to obtain a resin composition with excellent surface gloss and transparency, it is necessary to blend a large amount of rubber fraction in order to impart complete impact resistance. Ninth, when compared to straight methacrylic resin, it tends to have lower toughness such as tensile strength and bending modulus, as well as lower heat resistance, surface hardness, flow processability, etc. On the other hand, the latter blended resin composition has better toughness such as tensile strength and bending modulus, and has better impact resistance than straight methafuryl resin, but it has poor transparency and surface gloss. A slightly inferior tendency was observed.

As another method, a method has been proposed in which a vinyl yarn monomer is grafted in the presence of 281 acrylic (9) ester rubber latexes with different particle size ranges (Japanese Patent Publication No. 5B-45446). ), but in this method, the degree of grafting of vinyl monomers to rubbers containing different particle sizes of Class 2a is different, and nitrile-based or aromatic-based LILt forms are preferable for grafting. For this reason, when it appears as a methacrylic resin, it is unsatisfactory in terms of optical properties, etc., and is not practical.

[Problems to be Solved by the Invention J] The purpose of the present invention is to eliminate the above-mentioned drawbacks, and to solve the inherent characteristics of methacrylic resin such as transparency, surface appearance, moldability, heat resistance, mechanical strength, etc. The object of the present invention is to provide a methacrylic resin composition that imparts excellent impact resistance without impairing the properties of the methacrylic resin composition.

[Means for solving problems]

The inventors of the present invention have conducted intensive studies to completely eliminate the following drawbacks, and as a result, in a methacrylic resin composite sole containing two types of special rubber-like particles with different internal structures and particle sizes,
It has been found that the intended purpose has been achieved, and the impact-resistant methacrylic resin set 1 of the present invention has been completed.
0.110 to 90% by weight of methacrylic resin containing methyl methacrylate as a main constituent unit, rubber fraction [D] and rubber fraction CI] Ill 9 0. ~10% by weight, the resin composition comprising (A);
The rubber component CI is at least -169,9-89 acrylic acid alkyl ester in which the alkyl group has 2 to 8 carbon atoms.
．． 97Lf width, styrene is a mixture of styrene and its derivatives 30-100-10% by weight of sulfuric acid, methacrylic acid,
at least one acid component selected from the group consisting of cinnamic acid, sorbic acid, cyanuric acid, isocyanuric acid, maleic acid, succinic acid, phthalic acid, isophthalic acid and trimellitic acid, and allyl alcohol and methallyl alcohol. 201 to 5% by weight of a polymerizable polyfunctional substance (b) that is an ester with at least one unsaturated alcohol component, 0 to 5% by weight of other copolymerizable polyfunctional monomers, and other copolymers In the presence of the first step (a) of polymerizing 100"jjL parts of a monomer mixture consisting of 0 to 20% by weight of methyl methacrylate, 80% to 100% by weight of methyl methacrylate is added.
A monomer te consisting of this and a copolymerizable monomer 20 to 0 parts by weight is used in an internal process consisting of two steps: a second step Cb) in which 10 to 100 parts by weight of the mixture is polymerized. (B): Rubber component [I0. ] contains 40% by weight or more of methyl methacrylate units, and the total number of methyl methacrylate units and at least 1a units selected from acrylic acid alkyl esters having an alkyl group of 1 to 8 carbon atoms is 8.
The first step (c) is a polymer containing 0.03 it% or more.
In the presence of 60X parts, at least -4169,
8 to 89.9% by weight, styrene and its derivatives 30 to 100 to 10% by weight, 1 to 5% by weight of a copolymerizable polyfunctional substance (α), and other copolymerizable polyfunctional monomers. mer cL 1-5% by weight and other copolymerizable monomers O-20
11! , a second step (d) of polymerizing 99 to 40 fi parts of a monomer mixture consisting of '? and then the first step (
C) inside the particles (in the presence of 100 parts by weight of a two-layered rubbery material constituting the outer shell, 80 to 100x% by weight of methyl methacrylate, a copolymerizable polyfunctional monomer) Monomers consisting of 0 to 5 parts by weight of copolymerizable monomers and 0 to 20% by weight of other copolymerizable monomers, in any ratio within the above range, - several times. (C): Rubber component (the particle size of flll is the same as that of the first stage). (a)
In the second stage (d), the particle size of α05-0.15 μm1 rubber component is (L18-145 pm,
D): Rubber component 0.13 and rubber fraction CI [i of Il
The Philippine army is [I2) / [:D1] = 1/6~6/
1, and (gradient: a blend of methacrylic resin [r], rubber component (It) and CII [,), first mix rubber component [■] and rubber component [llff], and after t, methacrylic resin 0 The method of blending with methacrylic resin [[] Rubber component (II), methacrylic resin 0.
) and the rubber component [■] are individually mixed and then blended.

[Preferred embodiments of carrying out the invention]

The methacrylic resin [I] containing methyl methacrylate as a main structural unit used in the present invention is methyl methacrylate 80 to
The 100% by weight and 0 to 20% by weight of other vinyls are polymers of vinylidene monomers, such as acrylic acid alkyl esters having alkyl groups of 1 to 4 carbon atoms.

In the present invention, two types of rubber components [■] and a rubber component CIIIJ t- having different internal structures and particle sizes are used.

In the present invention, the first stage (aJ and the second stage (d) of the rubber fraction [river] of the rubber component 0.1) is an acrylic acid alkyl ester whose alkyl group has 2 to 8 carbon atoms, preferably At least one of n-butyl acrylate and 2-ethylhexyl acrylate 69.9 to 89.9
m (first stage (a)) is 698-89.8% by weight (
Second step (d)) 30-10 g 1% of styrene alone or a mixture of styrene and its derivatives, acrylic acid, methacrylic acid, cinnamic acid, sorbic acid, cyanuric acid, isocyanuric acid, maleic acid, succinic acid, phthalic acid, At least one acid component selected from the group consisting of isophthalic acid and trimellitic acid and at least one of allyl alcohol and methacrylic alcohol 69.9-89.9% by weight (first step (a)) or 69.8-89.9% by weight 89.8% by weight (second stage (A)), styrene alone or a mixture of styrene and its derivatives from 30 to 10 heavy JI[, acrylic acid,
't' selected from the group consisting of methacrylic acid, cinnamic acid, sorbic acid, cyanuric acid, isocyanuric acid, maleic acid, succinic acid, heptalic acid, isophthalic acid, and trimellitic acid;
A polymerizable polyfunctional substance (α) which is an ester of at least one acid component and at least one unsaturated alcohol fraction of allyl alcohol and methacrylic alcohol.
α1-5 1% by weight, 0-5% by weight of a crosslinkable monomer copolymerizable with these and having at least 2 carbon-carbon double bonds (first step (a)) or 01-5N! % (second stage (d)) and other copolymerizability ratios of 0 to 20%.

The composition ratio of the acrylic acid ester monomer and styrene or a mixture of styrene and its derivatives is one of the important factors for the resin composition of the present invention to have a high degree of transparency. Transparency decreases outside this range.

The polymerizable polyfunctional substance (α) is also one of the most important factors constituting the present invention, and thereby achieves the object of the present invention. Although the details of its action are not clear, the first stage (a) of the rubber component [■] and the second stage of the rubber component [III] (the degree of crosslinking of Q and the graft polymerizability with methyl methacrylate are well-balanced). It is presumed that this is because it is controlled. Although the appropriate amount of addition differs depending on whether it is used alone or in combination,
11-5] (The range of quantity coefficient is appropriate.

The polyfunctional monomer used here is not particularly limited, and various types can be used, such as ethylene glycol (meth)acrylate, 1,3-butylene di(meth)acrylate, and tetraethylene. Examples include glycol di(meth)acrylate and divinylbenzene.

The composition of the first stage (C) of the rubber fraction [m] is methyl methacrylate units 1r:40:! It is a polymer containing 1% or more of tJ, and moreover, a total of 80% or more of methyl methacrylate units and at least one unit selected from acrylic acid alkyl esters having 1 to 8 carbon atoms in an alkyl group.

As described above, the present invention provides the first stage (C
) The desired resin composition can be obtained by adjusting the specific composition. Next, as the first step (c) of the rubber component [III], examples of preferred embodiments will be described in detail, but this does not limit the present invention.

An example of the composition of the first stage (C) of the rubber component ClID is: - Methyl methacrylate units 80 to 100i, total polymerization of 20 to 0% by weight of acrylic acid alkyl ester units having 1 to 8 carbon atoms in the alkyl group; (1) 60 to 85% by weight of methyl methacrylate units, 5 to 20% by weight of ncrohexyl methacrylate units, and 1 acrylic acid alkyl ester unit having an alkyl group of 1 to 8 carbon atoms.
A copolymer consisting of 0 to 20% by weight, (1) 50 to 70% by weight of methyl methacrylate units, 10 to 20 weight percent of benzyl acrylate units, and 20 to 20 to 20 of acrylic acid alkyl ester units having an alkyl group having 1 to 8 carbon atoms;
A copolymer consisting of 30% by weight, etc. can be mentioned.

In ① to ③, from the above monomer mixture further containing a crosslinkable monomer consisting of a polyfunctional monomer having two or more acryloyloxy groups and/or methacryloyloxy groups in one molecule, the weight ratio is 1l11 to 1011L. It is more preferable to use a copolymer as follows. Examples of polyfunctional monomers include, but are not limited to, ethylene glycol di(meth)acrylate, 1,3-butylene di(meth)acrylate, 1.
Examples include 4-butanediol di(meth)acrylate.

Rubber component CID and rubber component 0.1D in the present invention
In the presence of the first stage (a) of the rubber component [ID or the second stage (d) containing the first stage (C) of the rubber fraction CI [I] inside the particles, The nine monomers are completely polymerized as a monomer mixture. Rubber component [I
The component composition of the monomer mixture in the second step (b)) of rubber fraction [I] and the third step (e) of rubber fraction [I] is 80 to 100 TJ amount of methyl methacrylate. Person in charge,
and other vinyl monomers copolymerizable with Koku 0 to 2
It consists of 0% by weight or less, and the rubber component [III]
In the third stage (fl2), the first stage (a) of the rubber fraction 0.1] and the second stage (fl2) of the rubber component CIII)
It is also possible to copolymerize 0 to 5 parts by weight of the same type of polyfunctional monomer as used in d), depending on the purpose.

Examples of other vinyl monomers that can be copolymerized with methyl methacrylate include styrene, acrylonitrile, and methacrylic acid; particularly preferred are acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, and butyl acrylate. . 72. The content of methyl methacrylate in the monomer mixture is 800
If the amount is less than 10% by weight, properties such as transparency and heat resistance will be poor. If the total amount of monomers other than acrylic ester exceeds 10% by weight, it is unfavorable in terms of transparency, heat resistance, water resistance, etc.

Rubber component CI0. ] In the production of
In the production of the third step (e) carried out in the presence of the second step (d), it is also possible to polymerize in several steps, for example by adding a polyfunctional monomer or a degree of polymerization regulator. When using a patterned polymer mixture, a crosslinking monomer or a degree of polymerization regulator can be added and the polymerization can be carried out separately into a skin portion and a portion to which it is not added.

That is, in the presence of the first stage (C) k particles and the second stage (d) 100] (in the presence of 100% by weight, first 80 to 100% by weight of methyl methacrylate, a copolymerizable polyfunctional monomer or Polymerization degree regulator such as mercaptan 0 to 5]
[% by weight, other copolymerizable monomers O~20] After the third step (81) of total polymerization of 100 parts by weight of a graft-crosslinkable monomer mixture consisting of 1% Uf, 80 parts by weight of methyl methacrylate
~100 parts by weight, 0 to 20% by weight of other copolymerizable monomers, or 0 to 1% by weight of a degree of polymerization regulator. A method consisting of two steps, the third two steps (e2) of polymerizing is preferred. In this case, the weight ratio of the third stage (e2) and the third two stages (e2) is (e2) / (e2) =
It is preferably 1/3 to 1/999.

The higher the molecular weight of the third stage (8) of the rubber fraction CII [], the more advantageous it is for impact resistance, but on the other hand, it may lead to a decrease in fluidity and a decrease in surface appearance characteristics.

On the other hand, when the molecular weight is small, fluidity and surface appearance characteristics are good, but impact resistance may be reduced. Depending on the case, a part of the third step (8) may be crosslinked to make the molecular weight higher, and the remaining part may be non-crosslinked to lower the molecular weight, resulting in a composition with excellent impact resistance, flow processability, and surface properties. It can also be a thing.

Rubber component [first stage (C) and second stage (d) of [[I]
The weight ratio of (c) / (d) = 1 to 60 / when the total of (C) and (d) is 100 parts by weight.
99 to 40 parts by weight, more preferably 5 to 50/95
~50 TL parts.

Second stage (b) of rubber component [■] b and rubber fraction CI
[The third stage (e) of
It is necessary to polymerize A to 10 to 1000 parts by weight per 100 parts by weight of the second step (d) in which C) is contained inside the particles. If the amount is less than 10 parts by weight, the improvement in impact resistance will be small and the surface gloss will be reduced (72:), which is not preferable. On the other hand, if it exceeds 1,000 parts by weight, productivity decreases, which is not preferable.

The rubber fraction used in the present invention [second stage (b) of ID]
), rubber component [I0. The hard resin segments and methacrylic resin [I'' in the first stage (C) and third stage (b3) of . It is desirable that the compositions of the regular polymers, excluding all auxiliary agents and crosslinkable single components, be the same or very similar. However, the first stage (a) of rubber component CI3 and the second stage (a) of rubber component [III]
It is also preferable that the refractive index of the one-stage elastomer mainly composed of alkyl acrylic ester (cL) is made to be very similar to that of the hard resin segment.

Further, during polymerization of each of the above-mentioned monomers or monomer mixtures, a degree of polymerization regulator such as mercabutan for adjusting the molecular weight can be used as necessary. Examples of polymerization degree regulators that can be used include alkyl mercaptans,
Examples include thioglycolic acid and its esters, β-mercapto-10-pionic acid and its esters, and aromatic mercaptans such as thiophenol and thiocresol.

One of the particularly important factors in the methacrylic resin composition of the present invention is a rubber component of 0.1] and a rubber component of 0.1
] There is a range of particle sizes. That is, the first stage (a) of the rubber component [■], the second stage (d
), the particle diameter is 105 to α15 μm, α
It is necessary to keep the thickness in the range of 18 to 0.45 μm. The resin composition of the present invention cannot be obtained depending on the rubber component having a particle size other than the above.

The methacrylic resin composition of the present invention comprises methacrylic resin [I
D, rubber component CII] and rubber ash [III].

The total amount of the two types of rubber components blended with the methacrylic resin is VC10-90 in the methacrylic resin m composition! j1%
Then, the 'X quantity ratio of the rubber component ['' and the rubber bottom mark] is 0.
．． I/(b1) must be in the range of 1/6 to 6/1. Outside the above range, the properties of the resin m-parallel of the present invention will not be effectively developed.

The blend of the methacrylic resin and the rubber component is first made by adjusting the rubber ash content CID and the rubber fraction CI0. ] and methacrylic resin [method of blending with ID, or methacrylic resin C1l and rubber a [jl], methacrylic resin 0. ]
and the rubber component Cn1)t-n must be mixed individually and then blended. Methods other than this method, such as methacrylic resin 0.
], rubber component [■] and rubber component 0. ] If they are mixed at the same time, uniform mixing will not be achieved and uneven dispersion (
(sphere splitting phenomenon) may occur, which is likely to cause the characteristics of the obtained n-th grade resin composition to be blurred.

In addition, the relationship between the total weight (6) of each blend component during blending and the internal volume (V') of the device used for blending is expressed as (m
/ (V) is preferably in the range of 0.05 to n 75 (Kg/l). If this range increases, disadvantages may occur such as the blend becoming non-uniform and adhesion to the wall of the blending device, making it difficult to obtain the desired methacrylic resin composition. The temperature during blending is
Rubber fraction [ID and rubber component 0.0. ] Except when co-coagulating by blending latex together, each blend/component is blended in powder, piece, or mfl pellet form using a known blender such as a V-shaped tumbler or Henschel mixer. In case 1c, the temperature inside the blending device is 70°C or less, particularly preferably 0°C to 50°C.
It is desirable that the range be within the range of . There is no particular good luck if the temperature is below 0℃, but the merits of keeping it below 0℃ are not clear. However, at temperatures above 70°C, the rubber fraction CIII and the rubber ash [I[[
) may stick, making it difficult to obtain a uniform methacrylic resin composition.

Since it is particularly preferable that the rubber ash [■] and the rubber fraction [llID] be produced by emulsion polymerization, an example in which the emulsion polymerization method is used will be described below.

After adding deionized water and an emulsifier if necessary into the reaction vessel, the rubber component was 0.11D and the rubber ash content was 0. The monomers (mixture) constituting the first stage of nl are polymerized, and then the monomers (mixture) constituting each second stage are added and polymerized in the presence of the first stage. Furthermore, the rubber component is 0.1
Regarding 1], in the presence of the first and second stages, the monomers (mixture) constituting the entire third stage are added and polymerized.

The polymerization temperature is 30 to 120°C, more preferably 50 to 1
It is 00℃.

The polymerization time depends on the type and amount of the polymerization initiator and emulsifier,
Although it varies depending on the polymerization temperature, etc., the time required for each polymerization step is usually 5 to 7 hours.

The ratio of monomer to water is preferably in the range of monomer/water=i/20 to 1/1.

A polymerization initiator and an emulsifier are added to either or both of the aqueous phase and the monomer phase.

Regarding the method of charging each monomer in each polymerization stage, the monomers can be charged all at once or in portions, but the split charging method is more preferable from the viewpoint of heat generation during polymerization and the like.

The emulsifier can be used without particular limitation as long as it is an emulsifier that can be used appropriately, such as long-chain alkyl carboxylates,
Examples include sulfosuccinic acid alkyl ester salts and alkylbenzene sulfonates.

1) The type of initiator can be used without any particular limitation; water-soluble inorganic initiators such as persulfate and perboron may be used alone, and in combination with sulfites, thiosulfates, etc. It can also be used as a redox initiator. Redox initiators such as ferrous salts of organic hydroperoxides and sodium sulfoxylates of organic hydroperoxides, initiators such as benzoyl peroxide and azobisisobutyronitrile can also be used. Emulsion polymerization method The obtained polymer latex is coagulated and dried by a conventional method.

In order to mix the thus obtained n9 rubber component [■] and rubber component [■] with the methacrylic resin C11 to obtain the resin composition of the present invention, a method using melt mixing is ideal. Prior to melt mixing, in addition to the above-mentioned resin composition components, stabilizers, lubricants, plasticizers, dyes and pigments, redundant fillers, etc. are added as necessary, and after blending by the method described above, mixing rolls and screw type extrusion are carried out. 150℃~30 using a machine etc.
Melt and knead at 0°C.

By molding the thus obtained solid methacrylic resin composition using an extrusion molding machine, an injection molding machine, etc., a molded article having excellent transparency, surface gloss, and impact resistance is obtained.

〔Effect of the invention〕

The methacrylic resin composition of the present invention has transparency, surface appearance,
It has excellent original properties of methacrylic resin, such as weather resistance and flow processability, without loss of money, and also has excellent mechanical strength and impact resistance.

[Example] Hereinafter, the present invention will be described in more detail based on Examples. In the examples, parts represent xi parts, and tlI represents weight %.

Example 1. IA, IB, Comparative Example 1 (Production of υ rubber component 0., 1 (b-1) First step (a) manufacturing content loss sot stainless steel reaction vessel was first subjected to the following (a) and ←) After charging all the raw materials, blowing nitrogen under stirring to make it substantially free from the influence of rR accumulation, and then heating at 65°C.
The temperature was raised to 80°C, and the following raw materials (c) were added, and the temperature was further raised to 80°C, and the mixture was continued for 90 minutes.
Polymerization was carried out for 20 minutes to obtain an acrylic latex.

(a) Raw material deionized water 3o4N-5fy
Leuylsarconone sodium 1001F (5-LH
) Boric acid 100SF Soda carbonate 1 (b*1:N
-Acyl sarcosinate (Nikko Chemicals (dog-made)) Raw material butyl acrylate (BA) (80%) 4K
g Styrene (EIT) (b9%) 950
P7+) Le J Taku+) V-To (MA) (b%)
5Cl cumene hydroperoxide (OHP)
1st (c) Raw material Deionized water 500f Thorium formaldehyde sulfoquinate (hereinafter abbreviated as Rongalit) 50? The polymerization rate of BA in this polymerization was 98%, the polymerization rate of ST was 99%, and the particle size of the obtained A&latex was 0.08 μm as determined by absorbance method.

(b-2) Production of second step (b)) In the same reaction vessel containing the latex containing 10 Kg (b00 parts) of solid content from the first step (a), (2) Raw material deionized water 500 fS-LN

After adding 259 and stirring, the temperature was raised to 80℃ for 1
80 parts of the following raw material (e) was continuously added at a rate of 40 parts/hour. Thereafter, the polymerization was continued for another 1 hour to obtain a rubber component (Il) which is a graft copolymer in the form of t-latex.The polymerization rate of the monomer of the raw material (E) was 99.
It was over 5 inches.

(e) Raw material methyl methacrylate (MMA) (96,0chi) 768
01F Ethyl acrylate IA) (4tS) 3
20? Normal octyl mercaptan 2890H
P249 This latex gold is coagulated, washed and dried by the method described below to form a powder of a rubber component with a multilayer structure.

In a stainless steel container, 50 parts of 1.0 sulfuric acid solution were charged with 9 parts, and the temperature was raised to 85°C with stirring, and the previously prepared latex 2
5 kg was added continuously over 15 minutes, and then the internal temperature was raised to t-90°C and held for 5 minutes. After cooling to room temperature, the polymer was separated by F and washed with deionized water to obtain a white creamy polymer, which was dried at 76°C for 36 hours to obtain a white powdery polymer.

(2) Production of rubber component (:I [I-1:] (2-1) First step (C) production In a stainless steel reaction vessel with an internal volume of 50 tons, the following (F-1) was first added. After adding the raw materials and blowing nitrogen under stirring to make it substantially free from the influence of oxygen, the temperature was raised to 70°C, all of the raw materials listed below (1) were added, and polymerization was carried out for 2 hours. 9. Obtain latex of hard crosslinked resin body.

(F-1) Raw material deionized water 2oyu5-LN
16 is boric acid
80f carbonated soda 8chi MMA
(97th Section) 19401FBA
(b4) 2091.3
-Butylene dimethacrylate (BIMAX2)
40 f (W-1) (deionized water 500 filtered potassium sulfate (KPS)) 24 t (2-2) Production of second stage (d) The polymerization of the above ('2-1) has been substantially completed. 2 in solids
Into the container containing the hard crosslinked resin latex in an amount equivalent to 0 parts, add the aqueous solution of the following (Chi 1) and raise the temperature to 80°C, then add the raw material tl-15 of the following (b7-1)
Add continuously for 0 minutes. After addition, 3 more
By continuing the polymerization for a period of time, an acrylic elastic latex with a nine-layer structure containing a hard crosslinked resin inside the particles was obtained.

(Chi 1) Raw material 5-LN
301F Rongaritto
32? deionized water
5001F (Ku 19 raw material BA (80%) 6400tS
(b8%) 14aaf allyl cinnamate (AOM)
(b, 5%) 96t1.4-butanediol diacrylate (C:4-DA) (0.5%)
52ft-butyl hydroperoxide (
TBH) 23P In the above case, the polymerization yields of BA and ST were 97% and 995% or higher, and the results were determined by absorbance method, and the particle size of the latex obtained was α26~α28 μm. .

(2-3) Production of the third step (+3) Into the above container containing latex gold equivalent to 100 parts of solid content obtained in the above polymerization (2-2), an aqueous solution of the following (Nu 1) was placed. was added and stirred, and then the following monomer mixture (Route 1) was continuously added over a period of 2.5 hours. Thereafter, the polymerization was continued for another 1 hour, and rubber component 1:ll1-1]
't - Available in latex form. The polymerization yield of MMA in the monomer mixture was 99.5% or more.

(Nu 1) Raw material 8-LN 201F deionized water 500t (Lou 1) Raw material MMA (96%) 4800fKA
(4ch) 200t normal octyl mercagutan (n-(4EIH) I Z5 fTBH5? This latex was coagulated, washed, and washed by the method described below.
After drying, the rubber component is 0.0. -1) The total amount of powder obtained is as follows. That is, 91f of 1.0 sulfuric acid water 60% in a stainless steel container.
The temperature was raised to 80°C while stirring, and 9t-
Continuous addition for 20 minutes, after which the internal temperature was increased to 95.
Raise the temperature to ℃ and hold for 5 minutes. After cooling to room temperature, the polymer was separated from P and washed with deionized water to obtain a white cream-like bomber. (3) Using the same reactor used in production (2) of rubber bottom content 0.1[-2,1~[:l[[-4], first (to-2)
The following raw materials were prepared and stirred (He-2A).
) was added all at once to the monomer mixture 80Z4f, and nitrogen gas was poured into the mixture to create a state substantially free from the influence of chlorine.
The temperature was raised to 70°C, the following raw materials (1) were added, polymerization was carried out for 60 minutes, and then monomer mixture 120i6f of (2B) shown in Table 1 was continuously boiled for 30 minutes. 〇 (He-2) Raw materials Deionized water 259■-Lauroylsarconosodium 8t (hereinafter referred to as rs-
Nitric acid 100 Sodium carbonate 102 Ferrous sulfate 0.01 t Ethylenediamine-4-acetate-2-sodium 1042 (r E
After raising the temperature to 80°C (referred to as DTA-2Na J), the following raw materials ()-2) were added, and to this, the following raw materials (Q-2) were continuously added over 150 minutes. After addition,
Polymerization was continued for a further 3 hours to obtain a latex acrylic elastic material with a multi-layered structure contained within all the particles of the hard crosslinked resin.

()-2) Raw material 5-LN
ICl Rongalit 32?
Deionized water 5002 (Chi 2)
Raw material BA (80chi) 51205
'ST (b)%) 1152
S' allyl cinnamate (AOM) (b, 5%)
9621.4-Butanediol diacrylate
322 (C!4-DA) (α5chi) C-butyl hydroperoxide (TBH)
23S' In the above case, the polymerization yields of BA and 3T are f'L97 and 99.5 or higher, respectively, and the particle size of the obtained Am latex is 0.26 to 1128 μm as measured by absorbance method. Atatsu nine.

(3-3) Production of third step (8) Pour the latex equivalent to 100 parts of solid content obtained in the above polymerization, then add the aqueous solution of 5 below (IJ-2) into the above container and stir. After that, the following monomer mixture (Nu 2) was added continuously for a total of 2.5 hours. After that, the treatment was continued for 1 hour, and the rubber was collected in the form of latex.

The polymerization yield of MMA in the monomer mixture was 99.5% or more.

i-2) Raw material sarcosinate L N 205' deionized water 500t (nu 2)
Raw material MMA (96chi) 480CIKA
(4%) 2oor normal octyl mercaptan (n-0@SH) 115 TBH59 This latex was coagulated, washed, and
Dry to obtain powder of rubber component [II].

That is, in a stainless steel container, 9'i of 1.0 sulfuric acid solution was added, the temperature was raised to 80°C with stirring, and the temperature was raised to 35K for Latin 2F.
G'i was added continuously for 20 minutes, then the internal temperature was raised to a total of 95°C, held for 5 minutes, and cooled to room temperature. This was dried at 70° C. for 24 hours to obtain a white powdery polymer.

(4) Methacrylic resin 0. -1 and Cl-2] Production of methacrylic resin 0. ], a bead-shaped polymer having a methyl methacrylate/methyl acrylate ratio of 9971 and a reduced viscosity of α060 (l/7) in chloroform was produced by the known suspension 1 method. This'k[+
−1]. Also, a bead-shaped polymer was produced in which the ratio of methyl methacrylate to methyl acrylate was 90/in and the reduced viscosity in chloroform was αossst7y. This is designated as Cl-2].

(5) Production of methacrylic resin m acid product n9 methacrylic resin Cl-1] obtained above, rubber component [
(2)] and rubber component [III] were blended by the method shown below. Use the rubber fraction shown in Table 21C.

Rubber component [■ 0.6Kg and rubber fraction ClID 1.4
[(W)/1.
tJ = (b1 (Yuz2)), the temperature in the tank was 35°C, and the stirring speed was 180 Orpm, and the mixture was blended for 3 minutes.

In addition, this blend and triphenylphosphite)
121Fi plus methacrylic resin [91 to I-112:
(W)z2)=0. 2 (K9/2)] All blended under the same conditions as above. The next polymer that adheres to the inside of the blending tank is a mixture of rubber fractions [0] and [III], IP, and methacrylic resin. -D was 22, and a blend with a uniform bottom was obtained.

The blend of the obtained n7t methacrylic resin composition was extruded into a cylinder using a screw extruder with an outer diameter of 40 mφ (manufactured by Nippon Seiso Co., Ltd., p-40-26AB-V type, L/D = 26). One temperature 2 (b0~260℃, die temperature 250℃
The pellets were melted and kneaded at 10°C to form pellets, and then injection molded under the following conditions. All of the test pieces obtained were evaluated, and the results shown in Table 2 were obtained.

Injection bottom molding machine = Nippon Steel Co., Ltd., V-17-65 type screw complete automatic injection molding machine Injection molding conditions Niji cylinder temperature 230-260 tl:,
Mold temperature 55°C Test piece size: 110mX 110mX 2m (thickness) 70mX 12. ．． 5 x & 2 (Thickness) The physical properties of the resin compositions in Examples and Comparative Examples were evaluated in accordance with the following method.

1. Heat distortion temperature (HDT°C) ASTM-D-6482,
MFR230℃, 10Kf? and 2301:.

5 8 to 9 ASTM-D-1238 5 Izot impact strength AEITM-D-256 (23
℃) Surface gloss (incident angle 60°) ASTM-D-673-44 s-Total light transmittance, haze ASTM-D-1003 & tensile strength and elongation ASTM-D-638 Reference example is [I-1] alone The evaluation results of the product are shown below.

From the results, the methacrylic 11 composition according to the present invention is
It can be seen that it has excellent surface appearance, excellent impact resistance, heat resistance, mechanical properties, and flow processability.

Examples 2, 3, 7, 7A, 7B, Comparative Examples 5 to 4 and Reference Examples 2 to 3 The results obtained in Example 1, methacrylic resin 0. ], rubber component [■
] and rubber fraction [:I [I] t-, the amount of each fraction used and blending conditions during blending are shown in Table 3.
A methacrylic resin composition was produced in exactly the same manner as in Example 1, except for the changes shown in Example 4. The evaluation results are also shown in Table 3゜4.
11] were blended with each other, and the rubber fraction [:
n] by the method recovered from the t-polymer latex,
Rubber component 0.1] and rubber component [III] were obtained simultaneously, and the subsequent steps were carried out in exactly the same manner as in Example 1 to prepare a molded article of the methacrylic resin composition. The evaluation results are also shown in Table-3. In this way, the rubber fraction [■] and cm
]'i A good methacrylic resin composition can be obtained even if blended at the latex stage.

Example 5 A methacrylic resin composition in the form of pellets obtained by the same method as in Example 1 was heated using a single screw extruder ((
[Co., Ltd.] Made by Thermo Glass Nack, 25 φ, vent type) S
(Manufacturing an extruded plate with a thickness of m) and conducting the same evaluation as in Example 1.

Example 6 In place of the super mixer used in Example 1, a rotary tumbler (Model 0M-25 manufactured by Odachi Seiko Co., Ltd., rotation speed 36) was used.
The procedure was as in Example 1 except for the following: (rpm, 30 minutes).

Examples 8-10. Comparative Examples 7-8 Examples and the first stage of rubber fraction [n] in one person (a
) and the particle scratching sound in the second stage (d) of the rubber fraction [I0.1], as shown in Table 3, were manufactured by changing the emulsifier in the initial stage of polymerization by changing the composition of the emulsifier. A methacrylic resin composition was produced and evaluated in the same manner as in Example 1 except for the above. The evaluation results are also shown in Table-5.

Example 11 In the production of the third step (e) of the rubber component 0.1 [-1] of Example 1, the type and amount of monomers constituting the third step (- and the polymerization method are shown below. A methacrylic resin composition was produced and evaluated in exactly the same manner as in Example 1, except for the following changes.The evaluation results are shown in Table 6.

(W-1) Raw materials M M A (96 壬) 477.5 fKA
(4%) 20t 1,4-butanediol diacrylate (b5%)2
．． 59TBH1,5P (War 1) Raw material MMA (96%) 43
209FhA (4%)
1801Fn-06SHIA5f TEH & 75 raw material (W-1) / Raw material (W-1) = 179 The polymerization method is to put the monomer of the above (W-1) into the latex money container obtained in 1 polymerization (2-2). After continuously adding the mixture t-30 minutes, the polymerization was continued for an additional hour.
0 Then, after continuously adding the monomer mixture of the above (War 1) for a total of 75 minutes, the polymerization was continued for an additional hour,
Rubber component lll-1] t'' obtained in the form of latex.

The polymerization yield of MMA in the monomer mixture was 99.5% or more. Examples 12 to 15. Comparative Examples 9-11 First stage (a) of rubber component [III] in Example 1
and the second step (d) of the rubber component [III] e. The methacrylic resin composition was prepared in exactly the same manner as in Example 11, except that the types and amounts of the constituent monomers were changed as shown in Table 7. A product was manufactured and evaluated. The evaluation results are also shown in Table 7, and from the results of 90 or more, the methacrylic resin composition according to the present invention has extremely good appearance characteristics (surface gloss, total light transmittance (fk
It can be seen that the material has excellent impact resistance.

Claims (1)

[Scope of Claims] 1) A resin composition consisting of 10 to 90% by weight of a methacrylic resin [I] whose main constituent unit is methyl methacrylate, and 90 to 10% by weight of a rubber component [II] and a rubber component [III]. (A); Rubber component [II] has an alkyl group having 2 to 2 carbon atoms;
69.9 to 89.9% by weight of at least one kind of acrylic acid alkyl ester of No. 8, 30 to 10% by weight of styrene or a mixture of styrene and its derivatives, acrylic acid, methacrylic acid, cinnamic acid, sorbic acid, cyanuric acid, isocyanuric acid. An ester of at least one acid component selected from the group consisting of acid, maleic acid, succinic acid, phthalic acid, isophthalic acid, and trimellitic acid and at least one unsaturated alcohol component of allyl alcohol and methallyl alcohol. Consists of 0.1 to 5% by weight of a polymerizable polyfunctional substance (α), 0 to 5% by weight of other copolymerizable polyfunctional monomers, and 0 to 20% by weight of other copolymerizable monomers. In the presence of the first step (a) of polymerizing 100 parts by weight of the monomer mixture, 80% to 100% by weight of methyl methacrylate and 20% to 0% by weight of a monomer copolymerizable therewith. (B); Rubber component [III] is methacrylic acid. A polymer containing 40% by weight or more of methyl units, and 80% by weight or more of a total of methyl methacrylate units and at least one unit selected from acrylic alkyl esters having an alkyl group of 1 to 8 carbon atoms. Certain first stage (c) 1-60
In the presence of parts by weight, 69.8 to 89.9% by weight of at least one kind of acrylic acid alkyl ester having an alkyl group having 2 to 8 carbon atoms, 30 to 10% by weight of styrene or a mixture of styrene and its derivatives, and the polymerization from 0.1 to 5% by weight of a polyfunctional substance (α), 0.1 to 5% by weight of other copolymerizable polyfunctional monomers, and 0 to 20% by weight of other copolymerizable monomers. A second step (d) of polymerizing 99 to 40 parts by weight of a monomer mixture consisting of Layer In the presence of 100 parts by weight of a rubbery substance, 80 to 100 parts by weight of methyl methacrylate, 0 to 5 parts by weight of a copolymerizable polyfunctional monomer, and 0 to 20 parts by weight of other copolymerizable monomers. The third step (e) consists of polymerizing 10 to 1000 parts by weight of a monomer or a mixture thereof at any ratio within the above range, once or in several times. (C); The particle size of the rubber component [II] is 0.05 to 0.15 μm in the first stage (a), and the particle size of the rubber component [III] is 0.05 to 0.15 μm in the second stage (a). d) is 0.18 to 0.45 μm, and (D
); The weight ratio of rubber component [II] and rubber component [III] is [II]/[III] = 1/6 to 6/1, and (E); Methacrylic resin [I], rubber component After mixing the rubber component [II] and the rubber component [III], the blend of [II] and the rubber component [III] is made by mixing the methacrylic resin [I].
or methacrylic resin [I] and rubber component [II], methacrylic resin [I] and rubber component [
III] by mixing each separately and then blending the two. 2) The impact-resistant methacrylic resin composition according to claim 1, wherein the first stage (c) of the rubber component [III] contains 80% by weight or more of methyl methacrylate units. 3) The third step (e) in the production of rubber component [III] is 80 to 99.9 weight % of methyl methacrylate in the presence of 100 parts by weight of the first step (c) and the second step (d);
Polymerize 1 to 100 parts by weight of a graft-crosslinkable monomer mixture consisting of 0.1 to 5% by weight of a copolymerizable polyfunctional monomer and 0 to 19.9% by weight of other copolymerizable monomers. The third step (e1) is a graft non-crosslinkable monomer or monomer mixture 9 to 9 consisting of 80 to 100% by weight of methyl methacrylate and 0 to 20% by weight of other copolymerizable monomers. It consists of two stages: a third two stages (e2) in which 999 parts by weight is polymerized, and a third stage (e1) and a third two stages (e2).
) composition ratio is (e1)/(e2) = 1/3 to 1/99
9. The impact-resistant methacrylic resin composition according to claim 1 or 2, which has an internal structure of: 4) In a blend of methacrylic resin [I], rubber component [II] and rubber component [III], the rubber component [II] and rubber component [III] are copolymers obtained by emulsion polymerization, The impact-resistant methacrylic resin composition according to claim 1 or 2, which is a polymer mixture that is simultaneously recovered after being blended in latex form at the polymer latex stage. 5) In the blend of methacrylic resin [I], rubber component [II] and rubber component [III], the ratio of the total weight (W) of the blend resin to the internal volume (l) of the blending equipment (W/
The impact-resistant methacrylic resin composition according to claim 1 or 2, wherein l) is 0.05 to 0.75 (Kg/l), and the temperature inside the tank during blending is 70°C or less. thing.