JPS6274946A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. having a high heat distortion temp. and excellent impact strength and transparency and giving a molding with an excellent appearance, by blending a styrene copolymer resin with a methyl methacrylate resin and a graft copolymer resin, each component having a refractive index within a specified range. CONSTITUTION:A resin compsn. is obtd. by blending 89-10wt% styrene resin (A) having a light transmittance of 80% or above, obtd. by polymerizing methacrylic acid monomer with styrene monomer or these monomers with further alpha-methylstyrene monomer with 1-80wt% methyl methacrylate resin (B) having a light transmittance of 80% or above and 10-50wt% graft copolymer resin (C) having a refractive index of 1.510-1.550 and a light transmittance of 60% or above, obtd. by polymerizing methyl methacrylate monomer with styrene monomer or these monomers with further acrylonitrile monomer in the presence of a rubbery polymer in a specified ratio in such a proportion that a difference in refractive index between the mixture of the resin component (A) with the resin component (B) and the resin component (C) is -0.005-+0.005.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a new and useful thermoplastic resin composition, and more particularly, the present invention relates to a new and useful thermoplastic resin composition. Comprised of copolymer resins, mainly applicable to molding processing,
The present invention relates to a resin composition that has a high heat distortion temperature and has excellent performance in impact strength, transparency, molded product appearance, etc.

[Problems to be solved by conventional technology and invention] Conventionally, polystyrene resin,
Styrene-acrylonitrile copolymer resins and methyl methacrylate-based resins are known, and these resins have excellent transparency, dimensional stability, electrical properties, and colorability, and are therefore used in a wide variety of fields. However, on the other hand, it is not necessarily satisfactory in terms of heat distortion temperature and impact strength, so it is being used in fields such as medical equipment, light electrical parts, and automobile parts that require such performance. The reality is that its use is restricted.

Therefore, in order to improve the heat distortion temperature, which is a drawback of polystyrene resin, conventionally, styrene monomer (hereinafter abbreviated as styrene) and methacrylic acid monomer (hereinafter abbreviated as methacrylic acid) were used. However, when using the styrene-methacrylic acid copolymer resin obtained in this way, which is a type of styrene-based copolymer resin, the heat distortion temperature in question is significantly improved. It cannot be denied that its uses are inevitably limited due to its inferior impact strength.

By the way, as a method for improving the GI impact strength of such styrene-based copolymer resin, it is generally known to mechanically mix a thermoplastic elastomer such as styrene-butadiene block copolymer resin. Styrene and methacrylic acid copolymer resin
When a butadiene block copolymer resin is mixed, although the impact strength is improved, there is an undeniable drawback that the transparency is significantly reduced.

On the other hand, in order to improve the heat distortion temperature and S impact strength of styrene-acrylonitrile copolymer resins and methyl methacrylate resins, when engineering plastics such as polycarbonate resins are mechanically mixed,
Although the heat deformation temperature and impact strength are improved, the difference in refractive index causes a significant decrease in transparency, and as a result, as disclosed in JP-A-49-353
It is not desirable to exhibit so-called pearlescent luster, as this would severely limit its use.

[Means for solving problems]

However, in view of the various drawbacks in the prior art as described above, the present inventors have improved the heat distortion temperature and impact strength, which are the drawbacks of polystyrene resin, and have also improved the heat distortion temperature and impact strength of polystyrene resin. In view of the drawbacks of methacrylate resins, such as a significant decrease in transparency caused by improving heat distortion temperature and impact strength,
After conducting intensive studies with the aim of solving these problems, we found that when methyl methacrylate resin is blended with a specific styrene copolymer resin, it can achieve a high heat distortion temperature without sacrificing transparency. A composition is obtained,
Moreover, the inventors have discovered the surprising property that a composition formed by blending both resins is homogeneous, and that a linear relationship is established between the refractive index of the composition and the blended weight ratio of both resins.

However, even with a composition made of such a specific styrene copolymer resin and methyl methacrylate resin, the impact strength is insufficient, The refractive index (J8; hereinafter the same) of a composition obtained by blending a specific graft copolymer resin and the specific styrene copolymer resin described above and a methyl methacrylate resin is such that the refractive index described above is 1,510 to 1.550, and the light transmittance (hereinafter the same) according to JIS K 6717 is within the range of ±0.005 of the refractive index of a specific graft copolymer resin of 60% or more. It has been discovered that by using such a resin composition, it is possible to achieve excellent heat distortion temperature, impact strength, and molded product appearance without significantly sacrificing transparency. The present invention was completed by discovering that the present invention can be applied to such specific fields. 9 That is, the present invention uses 20 to 50% by weight of methacrylic acid and 80 to 50% by weight of styrene.
or by copolymerizing methacrylic acid with
The light transmittance obtained by copolymerizing 50% by weight, 79 to 25% by weight of styrene, and 1 to 25% by weight of α-methylstyrene monomer (hereinafter abbreviated as α-methylstyrene) is Styrenic copolymer resin with 801 or more (
89 to 10% by weight of g) and 1 to 80% by weight of methyl methacrylate resin ω) having a light transmittance of 80% or more.
and 10 to 90 weight % of methyl methacrylate monomer (hereinafter abbreviated as methyl methacrylate) and 90 to 90 weight % of styrene in the presence of 20 to 80 weight % of the rubbery polymer.
or 5 to 49% by weight of methyl methacrylate in the presence of 20 to 80% by weight of the rubbery polymer.
90 to 1% by weight of styrene and 5 to 5% of acrylonitrile monomer (hereinafter abbreviated as acrylonitrile).
The refractive index is 1.510-1, obtained by copolymerizing 80-20% by weight of a mixture consisting of 0% by weight and 0% by weight.
550 and 10 to 50% by weight of the graft copolymer resin (C) having a light transmittance of 60% or more as an essential component, and the total of these (A), Q3) and (C) resin components is 100% by weight. - H, and the refractive index of the mixture of the resin component (A) and the resin component ω) in the above-mentioned specific ratio is -0 of the refractive index of the resin component (C),
It is an object of the present invention to provide a thermoplastic resin composition having a molecular weight within the range of 0.005 to +0.005.

As described above, it is an essential condition that the resin composition of the present invention contains the three components described above, styrene resin (A), methyl methacrylate resin (g), and graft copolymer resin (C). However, in a two-component system of ■resin component and ω) resin component, ■resin component and (C) resin component, or (can) resin component and (C) resin component, the expected result will never be achieved. The purpose is not achieved.

That is, the two-component system of (A) and (B) has insufficient impact strength as described above, the two-component system of (■) and C) significantly reduces transparency, and the two-component system of (03) and (C) Both of these two-component systems are unfavorable because the heat distortion temperature is significantly lowered.

In addition, styrene copolymer resin (A) and methyl methacrylate resin (A), which are components constituting the resin composition of the present invention, are also used.
Instead of using B), a styrene/methacrylic acid/methyl methacrylate ternary copolymer resin obtained by copolymerizing styrene, methacrylic acid, and methyl methacrylate is used to graft the ternary copolymer resin. Blending with copolymer resin (C) is not preferable because silver or flash will occur on the surface of the molded product during injection molding, significantly impairing the appearance of the molded product.

Furthermore, by using the resin composition of the present invention, excellent properties such as heat distortion temperature, impact strength, and appearance of molded products can be achieved without significantly sacrificing transparency.

Here, the above-mentioned styrene-based copolymer resin is composed of 20 to 50% by weight of methacrylic acid and 80 to 50% by weight of styrene, or 20 to 50% by weight of methacrylic acid, 79 to 25% by weight of styrene, and α -Methylstyrene 1~
A resin with a light transmittance of 80% or more obtained by thermal polymerization (bulk polymerization), solution polymerization, emulsion polymerization, or suspension polymerization of 25% by weight in the presence of a chain transfer agent and a radical generator. do.

An example of the method for preparing the styrene copolymer resin (A) is 20 to 50% by weight, preferably 25% by weight of methacrylic acid.
-45% by weight of styrene and 80-50%, preferably 75-55% by weight of styrene, or 20-50%, preferably 25-45% by weight of methacrylic acid and 79-25% by weight of styrene. %, preferably 78~
30% by weight, 1 to 25% by weight of α-methylstyrene,
Preferably, polyvinyl alcohol, sodium polyacrylate, potassium polyacrylate, polyvinylpyrrolidone, methylcellulose, hydroxyethylcellulose, or Cal. In water containing a suspension stabilizer such as oxymethylcellulose, and a suspension aid such as sodium chloride, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium carbonate or sodium alkylbenzene sulfonate, 50 to 1
There is a method of carrying out suspension polymerization at a temperature of 50°C, preferably 80 to 140°C, but after completion of such polymerization reaction, dehydration, washing, and then drying can be performed before use, and if necessary, It is also possible to add an antioxidant or a lubricant, and then provide the product in the form of granulation using an extruder or the like.

Next, as the above-mentioned methyl methacrylate resin (B), a homopolymer of methyl methacrylate or 8
0% by weight or more of methyl methacrylate and various acrylic esters such as methyl acrylate, ethyl acrylate or butyl acrylate; various methacrylic esters other than methyl methacrylate such as ethyl, methacrylate, butyl methacrylate and cyclohexyl methacrylate; acrylic acid, methacrylic acid,
Examples include copolymers of methyl methacrylate and various copolymerizable monomers such as styrene or acrylonitrile, but among these, resins with a light transmittance of 80 or more according to JIS K6717 are suitable and desirable. It is appropriate to use a homopolymer of methyl methacrylate.

As an example of the method for preparing the methyl methacrylate resin, methyl methacrylate alone or a monomer containing methyl methacrylate together with methyl methacrylate can be used.
Examples of methods include bulk polymerization, solution polymerization, or suspension polymerization using a seed or two or more kinds in the presence of a chain transfer agent and a radical generator, and general commercial products that can be used for molding seeds. Of course, it is possible to use -it.

Furthermore, the above-mentioned graft copolymer resin (C) is a mixture consisting of 10 to 90% by weight of methyl methacrylate and 90 to 10% by weight of styrene in the presence of 20 to 80% by weight of a rubbery polymer. or 20 to 80% by weight of the rubbery polymer.
5-49% by weight of methyl methacrylate, 90-1% by weight of styrene and 5-5% by weight of acrylonitrile in the presence of
A refractive index of 1.510 to 1.550 obtained by copolymerizing 80 to 20% by weight of a mixture consisting of 0% by weight and 0% by weight.
These resins are within the range shown below and have a light transmittance of 60% or more.

The general graft ratio (branch portion weight divided by trunk portion weight) of the graft copolymer resin (C) thus obtained is suitably within the range of 0.2 to 1.2.

Here, the rubbery polymer is polybutadiene rubber, a homopolymer of butadiene, such as acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, or a vinyl monomer copolymerizable with butadiene. Copolymers and the like are used.

First, one of the conditions for the graft copolymer resin (C) is that its light transmittance should be 60 inches or more, but when using one with a light transmittance of less than 60 inches, is not preferred because as a result, the resin composition obtained from the resin component (2) and (B) and the resin component (C) will be significantly inferior in transparency.

Next, the resin component (C) has a refractive index of 1.5.
One of the conditions is that the refractive index of the component C) should be within the range of 10 to 1.550, but setting the refractive index of the component C) within this range is important because the refractive index of the component C) is an essential component of the composition of the present invention. The refractive index of the mixture of g) resin component and ω) resin component is within a certain range of the refractive index of the component C).
This is a necessary range in order to ensure that the refractive index of the component Q is within the range of 005.

In addition, in preparing the graft copolymer resin (C), known and commonly used polymerization methods such as emulsion polymerization, emulsion-suspension polymerization, solution polymerization, or bulk polymerization can be applied as is. Of course, general commercially available products used for resin compounding can be used as they are.

Here, the resin composition of the present invention contains 89 to 10% by weight of styrene copolymer resin (1), 1 to 80% by weight of methyl methacrylate resin (color), and graft copolymer resin (C) as essential components. 10 to 50% by weight of these (A)
, (B) and (C), the sum of the three essential components is 100f
The refractive index of the mixture formed by blending the styrene copolymer resin (A) and the methyl methacrylate resin (B), respectively, is 1.510. -0.005 to +0.0 of the refractive index of the graft copolymer resin C), where the moxibustion condition is that the refractive index is in the range of -1,550 and the light transmittance is 60 or more.
However, in the case of the graft copolymer resin (C), it is not preferable that the blending amount is less than 10% by weight because the impact strength decreases; If it exceeds t, the heat distortion temperature will drop significantly, which is not preferable.

Furthermore, each of the above-mentioned styrenic copolymer resins (T)
and the methyl methacrylate resin (B) have a refractive index that is higher than that of the graft copolymer resin (B) described above.
It is not preferable to use a material having a refractive index exceeding the range of ±0.005 of C) because the transparency will be extremely poor.

Styrenic copolymer resin (A) and methyl methacrylate resin color as described above) and graft copolymer resin (
In order to obtain the resin composition of the present invention using C) as an essential component, it is suitable to use a known and commonly used blending method, for example, a blending method by heating and melting using a roll, Banbury mixer or extruder. be.

The resin composition of the present invention further contains various known and commonly used additive components such as heat stabilizers, antioxidants, ultraviolet absorbers, colorants, lubricants, and antistatic agents.
) and C) as appropriate in the blending step of the three essential components,
Of course, you can add more.

[Use of invention]

The thus obtained thermoplastic resin composition of the present invention has excellent heat deformation temperature, impact strength, transparency, appearance of molded products, etc., and has a wide range of uses. , word processors, iron/water inks, lighting covers, circle tube connectors, and other home appliance parts; printer covers, 70. OA-related parts such as disc cases and copy machine sorters; Automobile-related parts such as light guide plates, instrument panels, and rung housings; Optical-related parts such as cameras and optical prisms; Medical-related parts such as dialyzers and animal cages; Electronics It is used in a wide variety of fields, including food containers such as microwave tableware.

〔Example〕

Next, the present invention will be explained in more detail with reference to Reference Examples, Examples, and Comparative Examples. In the following, all parts and times are based on weight unless otherwise specified.

Furthermore, the physical properties of the molded articles obtained in each of the Examples and Comparative Examples were evaluated in the following manner.

■ Heating deformation temperature Compliant with ASTM D-648 (264 pst).

■ Izot impact strength Compliant with ASTM D-256 (with 1/4 inch notch).

■Light transmittance Compliant with JISK-6717.

■ Appearance of the molded product Using an in-line scree injection molding machine with a cylinder temperature of 270°C, the mold temperature was set at 60°C, and a plate-shaped molded product with a length of 50 cm x width of 50 cm and a thickness of 3 cm was injection molded. The appearance of the resulting molded product was visually inspected for the presence or absence of silver streaks, flash, etc., and those where the occurrence of silver streaks or 7-latency seams were observed were marked "x". Those in which none of these were recognized were indicated as "○".

Reference Example 1 [Example of Preparation of Styrene Copolymer Resin Container] 2.
00011 distilled water and 10.00% each as a suspension stabilizer. Ii+ carboxymethyl cell
7009 styrene, 1
5011 of methacrylic acid, 2I of di-tart-butyl peroxyhexahydroterephthalate, 1g of 1@rt-butyl perbenzoate and 31 of α-methylstyrene dimer were successively added, and then 400
When the temperature was raised to 90°C while stirring at rpm, 1509 methacrylic acid was added at a constant rate over 6 hours,
After the addition was completed, the temperature was kept at the same temperature for 3 hours, and then heated to 120℃.
The temperature was raised to 0.degree. C. and maintained at this temperature for an additional 3 hours to complete the polymerization.

The granular copolymer thus obtained was washed, dehydrated, and dried to have a refractive index of 1.569 and a light transmittance of 8.
Five layers of the desired resin were obtained. Below 1. This resin (A-1
).

Reference Example 2 (Same as above) Polymerization was carried out in the same manner as Reference Example 1 except that styrene was changed to 6009 and the initial amount of methacrylic acid was changed to 250.
A target resin named No. 51 was obtained. Hereinafter, this will be referred to as resin (A-2).
It is abbreviated as

Reference Example 3 (Same as above) Into the same reactor as Reference Example 1, 2,001 g of distilled water was charged, and 1,011 g of carboxymethyl cellulose and 0.051 g of sodium dodecylbenzenesulfonate were added thereto by IW reaction. Then add 60011 styrene,
100.9 α-methylstyrene, 150 J' methacrylic acid, 2I peroxyhexahydroterephthalic acid-
di-tsrt-butyl, 1 g perbenzoic acid-t@rt-
Butyl and 4 g of α-methylstyrene dimer were sequentially charged, and the rest was carried out in the same manner as in Reference Example 1 to obtain a desired resin having a refractive index of 1.567 and a light transmittance of 85 inches.

Hereinafter, this will be abbreviated as resin (A-3).

Reference Example 4 [Graft copolymer resin (preparation example)] 1.900.9% distilled water was charged into a nitrogen-substituted 51 reactor equipped with a stirring device, and 50JF of 20% sodium tyrosinate aqueous solution as an emulsifier was also charged. -F@ quenched, butadiene rubber with a solid content of 57.4%
1,045.9 pieces of latex were charged.

Next, 84y of methyl methacrylate and 36g of styrene were charged together with 0.5g of tert-dodecyl mercaptan and 4g of tris(nonylphenyl)phosphite, and heated to 65°C while blowing nitrogen gas. At that point, 100 y of distilled water containing 2 g of potassium persulfate was added, and the temperature was subsequently raised to 70° C. From that point, 196.9 methyl methacrylate and 84.9 styrene were added to 2.0 g of distilled water. The mixture was added at 6 speeds over 5 hours, and after the addition was completed, the same temperature was maintained for 1.5 hours, then the temperature was raised to 80° C., and the temperature was maintained for 1 hour to effect emulsion polymerization.

Afterwards, it is coagulated with magnesium sulfate, washed,
Dehydrated and dried to obtain powdered target resin 4.
Hereinafter, this will be abbreviated as resin (C-1), and its refractive index was 1.523, and its light transmittance was 75 cm.

Reference example 5 (same as above) Instead of butadiene rubber latex, the solid content is 41
% butadiene-styrene copolymer rubber latex (styrene content = 25%) at 1,46:l, and the composition of the initial monomers was changed to 549: methyl methacrylate, 549: styrene, and 1211: acrylonitrile. A powdered target resin was obtained in the same manner as in Reference Example 1, except that the composition of the monomers charged at constant speed was changed to 1261 methyl methacrylate, 126 g styrene, and 28.9 g acrylonitrile. Below, this resin (
It is abbreviated as C-2), and its refractive index is 1,537.
And the light transmittance was 75 inches.

Reference Example 6 Resin (A-1) obtained in Reference Example 1 and light transmittance of 9
2% Sumipex-B MHJ (Methyl methacrylate resin manufactured by Sumitomo Chemical Co., Ltd.; hereinafter referred to as resin (
It is abbreviated as B-1). ] in various composition ratios, kneaded and extruded using an extruder with a diameter of 50 fiφ and a cylinder temperature of 240°C, and then the refractive index of each blend thus obtained was expressed as the Abb refractive index ( As shown in the following formula, there is a linear relationship between the refractive index of each compound and the blended weight ratio of resin (A-1) and resin (B-1). It was confirmed that this holds true.

That is, let X be the refractive index of the mixture consisting of these two resins, nl
When, K1=-0,076) CI + 1.569
CI) Reference Example 7 Resin (A-2) and resin (B-1) obtained in Reference ψsu2
were blended in various composition ratios and the cross-extrusion refractive index was measured in the same manner as in Reference Example 6. As shown in the following formula, the refractive index of each blend and these resins (A-2) and It was also confirmed that a direct relationship was established between resin (B-1) and the blended weight ratio of both resins.

That is, when the refractive index of the mixture consisting of these two resins is n2, ! 12 = -0,070x2 + 1.563
(n) Reference Example 8 Resin (A-3) and resin (B-1) obtained in Reference Example 3 were blended in various composition ratios, cross-extruded in the same manner as Reference Example 6, and the refractive index was adjusted to δ. ! 11, as shown in the following formula, the refractive index of each compound and these resins (A-3)
Similarly, it was confirmed that a linear relationship was established between the blended weight ratio of both resins and resin (B-1), as shown in the following equation.

That is, when t13 is the refractive index of a compound made of both of these resins, ns = -0,0741s + 1.567
(Ill) Examples 1 and 2 ±0.0 of the refractive index of the resin (C-1) obtained in Reference Example 4
Resin (A-1) and resin (B-1) were blended in a composition ratio as shown in Table 1 so that the depth was within the range of 05 and the depth was within the range of 1.518 to 1.528. , and further resin (
C-1) was also blended and kneaded and extruded using an extruder with a cylinder temperature of 240° C. and a diameter of 50 mm to obtain pellets.

Next, both of these pellets were individually dried at 105° C. for 3 hours, and then molded using an in-line screw injection molding machine to obtain respective test pieces.

The physical properties evaluated for both test pieces thus obtained are summarized in the same table.

Examples 3 and 4 Instead of resin (C-1), "Kane Ace n-56" having a refractive index of 1.521 and a light transmittance of 60% or more was used.
(fl, a graft copolymer resin manufactured by 'N Kagaku Kogyo ■; hereinafter abbreviated as resin (C-3))], and the composition ratio was changed as shown in Table 1. Except for this, a composition was obtained in the same manner as in Examples 1 and 2,
Both test pieces were prepared by kneading, extrusion, and drying, and the physical properties of each test piece were evaluated, and the results shown in the table were obtained.

Examples 5 to 7 Resin (A-2) and resin (B-1) obtained in Reference Example 2, and resin (C-1) obtained in Reference Example 4 or 5, respectively.
or resin (C-2) or resin (C-3), respectively.
) Resin (A-2) and Resin CB-1) were blended at the W rrZ ratio as shown in Table 1 so that the refractive index of the resin (C- 1), (C
-2) or (C-3) was also blended, and henceforth Example 1
A composition was obtained in the same manner as in 2 and 2, cross-wire extruded, and dried to prepare three types of test pieces.The physical properties of each test piece were evaluated, and the results shown by the company were obtained. .

Example 8 Instead of the graft copolymer resin (C-1'), a graft manufactured by Kane Ace B-22J C Kanebuchi Chemical Industry ■ having a refraction amount of 1.539 and a light transmittance of 60 inches or more was used. The same machine as Example 5 was used except that a copolymer resin (hereinafter abbreviated as resin (C-4)) was used and the composition ratio was changed as shown in Table 1. A composition was obtained, kneaded and extruded, and dried to prepare a test piece.
When the physical properties of the test pieces were evaluated, the results shown in the table were obtained.

Example 9 ±0.0 of the refractive index of the resin (C-1) obtained in Reference Example 4
Resin (A-3) and resin (B-1) were blended in a composition ratio as shown in Table 1 so as to fall within the range of 05, that is, within the range of 1.518 to 1.528, Furthermore, this resin (C-1) was also blended, and Examples 1 and 2 were used thereafter.
A composition was obtained in the same manner as above, mixed and extruded, and dried to prepare a test sand piece, and when the physical properties of the test piece were tested, the results shown in the table were obtained.

Comparative Example 1 2,450 parts of the resin (A-2) obtained in Reference Example 2 and 1.050 parts of the resin (B-1) were blended, and the diameter of the cylinder was 50@ The mixture was kneaded and extruded using an extruder IIφ, and the refractive index of the thus obtained mixture was measured and found to be 1.542.

Then, (A-2) and CB-1) in the amounts described above, respectively.
and the resin obtained in Reference Example 4 (C-1
) and 1.500 parts of
The mixture was kneaded and extruded using an extruder with a diameter of 50 mm and set at 0°C to obtain pellets.

Thereafter, this pellet was dried at 105°C for 3 hours and then molded using an in-twin screw injection molding machine to obtain a control test piece.The physical properties of the test piece were determined as shown in Table 1. Shown all together.

Comparative Example 2' 700 parts of resin (A-2), 2.80 parts of resin (B-1)
Nine pieces of control specimens were obtained in the same manner as Comparison f1+1 except that 0 parts and 1,500 parts of resin (C-1) were used, and the physical properties were evaluated, as shown in Table 1. The results shown are obtained.

The refractive index of the blend of both resins (A-2) and (B-1) in the above amounts was 1.507.

Comparative Examples 3 and 4 Resin (A-2) obtained in Reference Example 2 and resin (B-1)
Except that the resin (C-1) obtained in Reference Example 4 was changed to be used at the composition ratio shown in Table 1.
Control test pieces were obtained in the same manner as in Comparative Example 1, and the physical properties of each test piece were evaluated, and the results shown in Table 1 were obtained.

Comparative Examples 5 to 7 Resin (A -2) and resin (B-1), Comparative Example 5) or resin (A-
2) and resin (C-1) (Comparative Example 6), or resin (B-1) and resin (C-1) (Comparative Example 7), and Comparative Example 1 in the same manner as in Comparative Example 1. Prepare a test piece of
When the physical properties of each test piece were evaluated, the results shown in Table 1 were obtained.

Comparative Example 8 As an example of a case in which only the (A) resin component is present without the (B) &ll acid component and (c) resin component, Kuju FXfiJ (A-2) obtained in Example 2 was used in cylinder 11. degree 2
The pellets obtained by kneading and extruding with an extrusion tube with a diameter of Sowφ at 40°C, and then drying at 105°C for 3 hours were molded using an in-line screw injection molding machine to produce control test pieces. The test pieces were prepared and their physical properties were evaluated, and the results shown in Table 1 were obtained.

Comparative Example 9 (A) Resin component and (Q Resin component simply lacking (B)
) As an example of the case where only the resin component is used, except for changing to use resin (B-1) instead of resin (A-2),
A control test piece was prepared in the same manner as in Comparative Example 8, and the physical properties of the test piece were evaluated, and the results shown in Table 1 were obtained.

Comparative Example 10 A reactor similar to Reference Example 1 was charged with 2,000.9 g of distilled water, and 10 l of carboxymethyl cellulose and o s y of sodium dodecylbenzenesulfonate were added thereto as suspension stabilizers. -S and further added thereto 250I of styrene, 450F of methyl methacrylate), 15ON of methacrylic acid, 2# of di-tart-butyl peroxyhexahydroterephthalate, 1
11 tert-butyl perbenzoate and 4 g α-
Methystyrene dimer was sequentially charged, and the rest was carried out in the same manner as in Reference Example 1 to obtain a ternary copolymer resin having a refractive index of 1.525.

From now on, instead of resin (A-2) and resin (B-1),
A control test piece was prepared in the same manner as in Comparative Example 1, except that T was changed to use the same amount of the above ternary copolymer resin as the total amount of both resins, that is, 3.5009, and about the test piece. When the physical properties were evaluated, the results shown in Table 1 were obtained.

Comparative Example 11 The mixing ratio of the resin (Mu-2) obtained in Reference Example 2 and Asafure Kusu 810 J (styrene-butadiene-pro-resin copolymer resin manufactured by Mukasei Kogyo ■) was 50 parts = 50 The diameter of the cylinder with a temperature of 240℃ is 5.
Knead and extrude using an extruder with a diameter of 0.0 mm to make pellets.
Dry at 05°C for 3 hours, then reduce cylinder temperature to 2.
A control test piece was prepared by molding in an in-line screw injection molding machine set at 40°C, and the physical properties of the test piece were evaluated, and the results shown in Table 1 were obtained. It was done.

Comparative Example 12 50 parts of resin (B-1) and r Tubarex 7025A J (polycarbonate resin manufactured by Mitsubishi Chemical Corporation):
The mixture was blended at a mixing ratio of 50 parts, pelletized using an extruder with a cylinder temperature set at 280°C, and then dried at 120°C for 3 hours. The resulting pellets were placed in an in-line screw injection molding machine. A control test piece was prepared by molding the cylinder at a temperature of 250°C, and the physical properties of the test piece were evaluated.
The results shown in the table were obtained.

Comparative Example 13 Instead of resin (B-1), “Tyryl 783” [styrene-acrylonitrile copolymer resin manufactured by Mukasei Kogyo ■]
A control test piece was prepared in the same manner as in Comparative Example 12, except that the test piece was changed to use .

Comparative Example 14 "Tyryl 783" was dried at 90°C for 3 hours, then put into an in-line screw injection molding machine at 250°C.
A control test piece was prepared by molding the sample at a cylinder temperature of 1,000 yen, and the physical properties of the test piece were evaluated, and the results shown in Table 1 were obtained.

Comparative Example 15 "D-KUSTIREY xc-slo:" (polystyrene manufactured by Dainippon Ink & Chemicals) was molded using an in-line/screen-fII injection molding machine with the cylinder temperature set at 220°C. A test piece for comparison was prepared and the physical properties of the test piece were evaluated.
The results shown in the table were obtained. / [Effects of the Invention] As is clear from the results in Table 1, the thermoplastic resin composition of the present invention can It is known that it has a much higher heat deformation temperature and impact strength than copolymer resins.

Moreover, the composition of the present invention not only has much better transparency than conventional blend products, but also has polystyrene resin, methyl methacrylate resin, and styrene resin.
It is also known that, like acrylonitrile copolymer resin, it has a high degree of transparency with a 1-ray transmittance of 80 inches or more.

As described above, the thermoplastic resin composition of the present invention has excellent properties such as heat distortion temperature, impact strength, and transparency, as well as molded product appearance, and therefore has a wide range of applications. It can be used for inspection of various molded products as mentioned above.

Agent Patent Attorney Katsutoshi Takahashi Procedural Amendment 1985 Lθ Month 2 Interim Commissioner of the Patent Office Michibe Uga 1, Indication of the case 1985 Patent Application No. 217506 2, Name of the invention Thermoplastic resin composition 3. Relationship with the case of the person making the amendment Patent applicant: 3-35-58 Sakashita, Itabashi-ku, Tokyo 174 (28
8) Dainippon Ink & Chemicals Co., Ltd. Representative Yo Mura
Kuni Shigeru 4, Agent Address: 103, Dainippon Ink & Chemicals Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo Voluntary Office 6, “Claims” column of the specification to be amended ゛-゛～7 ,
Contents of amendment (1) The description of the scope of claims is corrected as shown in the attached sheet.

(2) The statement "Styrenic resin (A)" on page 9, line 3 of the specification is corrected to "Styrenic copolymer resin (A)."

(3) The description "Word Processor Sensor" on page 17, lines 10-11 of the specification is corrected to "Food Processor J."

(A) Statement on page 22, line 18 of the specification “Reference Example 1
" is corrected to "Reference Example 4j.

The above amended claims rl, (A) 20 to 50% by weight of methacrylic acid monomer and 80 to 50% by weight of styrene monomer, or 20 to 50% by weight of methacrylic acid monomer; JIS, obtained by copolymerizing 79 to 25% by weight of heavy ethylene monomer and 1 to 25% by weight of α-methylstyrene monomer.
89 to 10% by weight of a styrene copolymer resin with a light transmittance of 80% or more according to JIS K-6717; and (B) methyl tsutakuri with a light transmittance of 80% or more according to JIS K-6717. Rate resin 1-8
(C) of a mixture consisting of 10-90% by weight of methyl methacrylate mono I and 90-10% by weight of styrene monomer in the presence of 20-80% by weight of a rubbery polymer. 80
5 to 4% of methyl methacrylate monomer in the presence of ~20% by weight or 20 to 80% of the rubbery polymer.
The refractive index (
nl) is 1.510 to 1.550, and JIS K
-10 to 50% by weight of a graft copolymer resin having a light transmittance of 60% or more according to 6717 is an essential component, and the total of the above resin components (A), CB) and (C) is 100% by weight. %, and the refractive index (n'J) of the mixture of the resin component (A) and the resin component (B) in the above-mentioned specific ratio is the refractive index (n'J) of the resin component (C) above. n"+!') -o, o o s~+0.0
05.

2. The composition according to claim 1, wherein the rubbery polymer is a butadiene homopolymer.

3. Claim 1, wherein the rubbery polymer is a copolymer of butadiene and styrene.
The composition described in Section.

4. The composition according to claim 1, wherein the rubbery polymer is a copolymer of butadiene and acrylonitrile.

5. The composition according to claim 1, wherein the rubbery polymer is a copolymer of butadiene, styrene, and acrylonitrile. j or more

Claims (1)

Scope of Claims 1. (A) 20 to 50% by weight of methacrylic acid monomer and 80 to 50% by weight of styrene monomer, or 20 to 50% by weight of methacrylic acid monomer, styrene monomer 79-25% by weight of monomer and 1% of α-methylstyrene monomer
JIS K- obtained by copolymerizing ~25% by weight
(B) 89 to 10% by weight of a styrene copolymer resin with a light transmittance of 80% or more according to JIS K-6717, and (B) a light transmittance of 8 according to JIS K-6717.
1 to 80 of methyl methacrylate resin that is 0% or more
and (C) 80-90% by weight of methyl methacrylate and 90-10% by weight of styrene monomer in the presence of 20-80% by weight of a rubbery polymer.
5 to 49% of methyl methacrylate monomer in the presence of 20% by weight or 20 to 80% by weight of the rubbery polymer.
8% by weight of a mixture consisting of 90-1% by weight of styrene monomer and 5-50% by weight of acrylonitrile monomer.
Refractive index (n
_D^2^8) is 1.510 to 1.550, and JI
10 to 50% by weight of a graft copolymer resin having a light transmittance of 60% or more according to S K-6717 as an essential component, the sum of the above resin components (A), (B) and (C) is 100% by weight, and the refractive index of the mixture of (A) resin component and (B) resin component in the above-mentioned specific ratio is -0 of the refractive index of the above-mentioned (C) resin component. A thermoplastic resin composition, characterized in that the thermoplastic resin composition is within a range of .005 to +0.005. 2. The composition according to claim 1, wherein the rubbery polymer is a butadiene homopolymer. 3. The composition according to claim 1, wherein the rubbery polymer is a copolymer of butadiene and styrene. 4. The composition according to claim 1, wherein the rubbery polymer is a copolymer of butadiene and acrylonitrile. 5. The composition according to claim 1, wherein the rubbery polymer is a copolymer of butadiene, styrene, and acrylonitrile.