JPS60127345A - Methacrylic resin composition - Google Patents

Abstract

PURPOSE:The titled composition, obtained by incorporating a crosslinked acrylic acid ester based copolymer with a compound selected from specific glycerides, etc., and having improved impact resistance and antistatic properties imparted thereto without deteriorating the original characteristics of the resin. CONSTITUTION:A methacrylic resin composition obtained by incorporating 50- 99.8wt% methacrylic resin containing >=80wt% methyl methacrylate units with 40-0.1wt% rubber component consisting of a crosslinked acrylic acid ester based copolymer and 10-0.1wt%, preferably 7-0.3wt% at least one compound selected from the group of compounds expressed by formulas I -VIII (R, R1-R9 are H or 8-20C alkyl; R16-R19 are 8-20C alkyl; R10-R15 are 1-18C alkyl; M, M1, M2, M3 and M4 are H, Na, K or Li; n is 1-50). Ethyl acrylate, butyl acrylate, etc. are used as the acrylic acid ester, and >=50% thereof is copolymerized.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a novel methacrylic resin composition, and more particularly to a methacrylic resin composition having excellent impact resistance and antistatic properties.

[Technical background of the invention and its problems] Conventionally, methacrylic resin has the inherent transparency,
Taking advantage of its excellent properties such as weather resistance, easy workability, and heat resistance,
It is used in fields such as signboard lighting equipment parts and vehicle exterior parts.

However, in such application fields, it is desired to improve the drawbacks of methacrylic resins, such as cracking due to insufficient impact resistance and adhesion of dust due to static electricity damage.

To date, there has been no proposal for a composition that maintains the original properties of methacrylic resin and improves the above two deficiencies at the same time, or a method for producing the same.

[Object of the Invention] An object of the present invention is to provide a novel methacrylic resin composition that has excellent impact resistance and antistatic properties without impairing the original properties of the methacrylic resin.

[Summary of the Invention] As a result of extensive research to achieve the above object, the present inventors have found that by adding a specific amount of a crosslinked acrylic ester copolymer and a compound having a specific structure to a methacrylic resin, a The inventors have discovered that a methacrylic resin composition with excellent impact resistance and antistatic properties can be obtained, and have completed the present invention.

That is, the present invention uses 50 to 88.8% by weight of a methacrylic resin (I) composed of 80% by weight or more of methyl methacrylate units and 20% by weight or less of other monomer units copolymerizable therewith.
and; 40 to 0.1% by weight of rubber component (II) composed of a crosslinked acrylic ester copolymer; and the following formulas A, B,
C, D, E, F, G and H: CH2-OR CH-OR+ (A) CH20R2 CH2-OR3 ■ R60CH2-C-CH2-0R4 (B) CH20R5 CH20R7 R90CH2C-CH2CH3 (C) Goose CH20Re Il 0M2 CHOH R饋CON (D) CH2CHOH R.

14 ■ CH2CHOH R, IN (E) CH2CHOH 15 00M RB　O(CH2CH20)n　P　(F)OM.

M3 R, OQ \KakuP-0M, (H) Rl, 0 (In these formulas, R+ R1+ R2* R3+ R4
iR5+ Ru + R7+ R8 and R9 may be the same or different, and each represents hydrogen or carbon a8-2o.
The alkyl group of Rm, R17, Ru and Ru
l* May be the same or different, carbon number 8~
2° alkyl group, R11+ Ru + Ru +
Ru + R & 4 and Ru may be the same or different from each other and represent an alkyl group having 1-18 carbon atoms, M, ・M + M 2 + Ms and M4 may be the same or different from each other Often represents hydrogen, Na, K and Li, where n is 1
It is characterized by comprising 10-0.1% by weight of at least one compound (m) selected from the group of compounds represented by ), representing a number of ~5o.

In the following, the invention will be explained in more detail.

The methacrylic resin (1) used is a polymer consisting of 80% by weight or more of methyl methacrylate units and 20% by weight or less of other copolymerizable monomer units. The content of copolymerizable monomer units is 20% by weight or less.
This is because, if it exceeds 100%, the properties such as mechanical properties such as heat resistance, water resistance, and tensile strength of the methacrylic resin (1) will deteriorate.

Monomers copolymerizable with methyl methacrylate include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate, methyl acrylate, and ethyl acrylate. , butyl acrylate, acrylic acid alkyl esters such as 2-ethylhexyl acrylate, styrene, acrylonitrile.

Methacrylic acid, acrylic acid, itaconic acid, maleic acid,
Examples include fumaric acid, vinyltoluene, etc., and preferably acrylic acid alkyl esters such as methyl acrylate, and styrene.

Rubber component (II
) is a component that works together with compound (m) to improve the impact resistance and antistatic properties of the methacrylic resin.

The crosslinked acrylic ester copolymer preferably contains in its structure a portion exhibiting elastomeric properties consisting of 50% by weight or more of polymerized acrylic ester units.

As the acrylic ester used here, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, etc. are particularly preferred, and 50% by weight or less of other copolymerizable monomers are added thereto. Can be copolymerized. Other copolymers used here include methacrylic acid alkyl esters such as methyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate, styrene, acrylonitrile, and the like. Although it is necessary to crosslink the aggregate, the crosslinking agent used is not particularly limited, but preferably ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1
, 4-butanediol diacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, etc., and these can be used alone or in combination.

The rubber component (II) may have any structure as long as it exhibits elastomer properties.For example, the rubber component (II) may have any structure as long as it exhibits elastomer properties. Whether the structure is composed of a compound (m
) is effective in imparting antistatic ability.

The amount of rubber component (II) added is 40 to 0.1 in the resin composition.
% by weight, preferably 35-0.5% by weight.

If it is less than 40% by weight, heat resistance is low, and if it is less than 0.1% by weight, impact resistance and antistatic properties are poor.

Compound (m) has the following formula A, B, C, D, E, 'F.

G and H: CH2-OR CH-01'll (A) CH2-0R.

CH20Ra Rs OCH2-C-CH20Ra (B) CH20
Rs CH20R7 R90CH2-c-CH2-CH3 (C) Summer CH20Re R.

0M2 CHOH RLlICON (D) CH2CHOH RL! ? +4 CH2CHOH RIS N (E) CH2CHOH If Ru　0-　(CH2CH20)n　P　(F)0M□ 　0M2 R170-P (G) OM.

P　OMa　(H) R1! 0 (In these formulas, R, R,, R2, Rs, R4.

R5r Ru r R7+ R8 and R9 may be the same or different from each other, and represent hydrogen or an alkyl group having 8 to 2 o carbon atoms, and Ru r Rht r R□ and R, may be the same or different from each other. Also, an alkyl group having a carbon number of 8 to 2° is + Ru + Ru + R* + Ru
*R14 and R, may be the same or different and represent an alkyl group having 1 to 18 carbon atoms, Ms, M++
M2, M3 and M4 may be the same or different and represent hydrogen, Na, K and Li, and n is 1 to 5o.
10-0.1% by weight of at least one compound selected from the group of compounds represented by ), representing the number of .

Even if substances other than those mentioned above are used, it is difficult to maintain the natural properties of the resin.

The amount of compound (m) added to the resin composition is 10-0.1% by weight, more preferably 7-0.3% by weight.

Outside this range, there will be drawbacks such as the surface of the final product of the resin composition becoming sticky or the antistatic effect not being exhibited.

The method for producing the methacrylic resin (I) used in the present invention is not particularly limited, but bulk polymerization or suspension polymerization is preferable.
Although there is no need to particularly limit the manufacturing method, emulsion polymerization is particularly preferred.

An example using the emulsion polymerization method will be described below.

After adding deionized water and an emulsifier if necessary to the reaction vessel, the crosslinked acrylate copolymer was added to 50ti i+-
To obtain copolymers containing 5 or more, the monomer mixture is polymerized in one or multiple stages.

The polymerization temperature is from 30 to 120"0, more preferably from 50 to
The zero polymerization time at 100°C varies depending on the type and amount of the polymerization initiator and emulsifier, the number of polymerization stages, the polymerization temperature, etc.
Usually, it is 0.5 to 20 hours.

The blending weight ratio of monomer and water is monomer/water = 1720-1
/1 is preferred.

The polymerization initiator and emulsifier can be added to either or both of the aqueous phase and monomer phase.

The method of charging the monomers in the polymerization operation can be carried out all at once or in portions, but it is basically preferable to charge the monomers in portions, although this may vary depending on the number of polymerization stages.

Emulsifiers do not need to be particularly limited as long as they are commonly used; examples of use include long-chain alkyl carboxylates,
These include sulfosuccinic acid alkyl ester salts and alkylbenzene sulfonate salts.

There is no need to particularly limit the type of polymerization initiator, and commonly used water-soluble inorganic initiators such as persulfates and perborates can be used alone or in combination with sulfites as redox initiators. . Also, redox initiator systems such as organic hydroperoxide-sodium formaldehyde sulfoxylate, benzoyl peroxide, azodosubutyronitrile, and other initiator systems can be used.

The crosslinked acrylic ester copolymer obtained by emulsion polymerization is coagulated and dried by a known method.

When blending the obtained methacrylic resin, rubber component (II) and compound (II), the most ideal method is to melt and mix them. Prior to melt mixing, in addition to the resin composition, stabilizers, lubricants, plasticizers, dyes, pigments, fillers, etc. are added as necessary, and the mixture is processed using a V-type blender, Henschel mixer, mixing roll, or screw type extruder. The mixture is melt-kneaded at 150 to 300°C.

The composition thus obtained can be molded using an extruder or an injection molding machine to obtain a molded article with excellent impact resistance and antistatic properties.

[Effects of the Invention] As is clear from the above explanation, in the present invention, the rubber component (II), which is a crosslinked acrylic ester copolymer, and the compound (m) work together to improve the impact resistance of the methacrylic resin (I). and improves antistatic properties. In the absence of the crosslinked acrylic acid ester copolymer (H), even if the compound (m) is contained in the methacrylic resin CI), not only is no impact resistance imparted, but the antistatic property is also extremely poor. Although the details of the mechanism of action are not clear, it is thought that the presence of the rubber component (11) whose glass transition point (Tg) is below room temperature facilitates the movement of the compound (m) in the composition. It is thought that this effect improves the dispersion state of compound (m) in the composition and also has a positive effect on the exudation of compound (m) onto the surface of the composition. However, the above-mentioned effect due to the presence of the rubber component (II) is exhibited only in a specific type of compound (m) according to the present invention.

As described above, the methacrylic resin composition of the present invention has excellent impact resistance and antistatic properties in addition to the original excellent properties of methacrylic resin, and its industrial applicability is extremely large.

[Embodiments of the invention] Hereinafter, the present invention will be explained in more detail based on Examples.

In the examples, parts refer to parts by weight, and % refers to % by weight.

[Dog] 11'' 5.7 kg of methacrylic resin (I) obtained by suspension polymerization of a monomer mixture of methyl methacrylate/methyl acrylate in a weight ratio of 88/1, 80% butyl acrylic, 1B% stinone, A first stage of polymerizing a monomer mixture consisting of 1% of acrylic methacrylate and 98% of methyl methacrylate in the presence of 100 parts of the product obtained in this first stage.
Rubber component (II) obtained by an emulsion polymerization method consisting of two steps in total: the second step of polymerizing 60 parts of a monomer mixture of 1% and 1% methyl acrylate.3. l3kg and stearic acid monoglyceride 0.4k as compound (m)
g were mixed in a Henschel mixer, and then extruded into pellets using a twin-screw extruder (PGM-301 manufactured by Token Tekko Co., Ltd., at a cylinder temperature of 190 to 250°C).

This was injection molded under the following conditions, and from the obtained test, the first
Table evaluation results were obtained.

Injection molding 41! = Made by Japan Steel Works, V-17-855 screw complete automatic injection molding machine Injection molding conditions Niji cylinder temperature 250 ° C, mold temperature 60
°C, injection pressure (gauge pressure) 50kg/cif Test piece size: 110 Xll0 X 2 (thickness)
(tw) 70X 12.5X 8.5 (thickness) (+1
11) As the 10-necked rubber component (II), methyl methacrylate/methyl acrylate/l, 9 of 3-butylene dimethacrylate
? The first step is to polymerize 25 parts by weight of a monomer mixture consisting of a weight ratio of butyl acrylate/styrene/acrylic methacrylate/, 3-butylene dimethacrylate, 80/18/1.0/1. a second stage of polymerizing 75 parts by weight of a monomer mixture consisting of a 0 weight ratio; a third stage of polymerizing 60 parts by weight of a monomer mixture consisting of a 89/1 weight ratio of methyl methacrylate/methyl acrylate; An injection molded product was obtained in exactly the same manner as in Example 1, except that a product obtained by apparatus polymerization consisting of three steps in total was used, and this was evaluated according to the method performed in Example 1. The results are shown in Table 2.

The first stage of polymerizing 10 parts by weight of a monomer mixture consisting of H,5/0.5° weight ratio of methyl methacrylate/acrylic methacrylate as the rubber component (n), methyl methacrylate/butyl acrylate/styrene The second stage also polymerizes 15 parts by weight of the mixture, consisting of monomers in the weight ratio of 50/40/11.5/acrylic methacrylate/acrylic methacrylate/80,718/1.0 weight ratio of butyl acrylate/styrene/acrylic methacrylate. The third stage of polymerizing 50 parts by weight of a monomer mixture, 10 parts by weight of a monomer mixture consisting of a so/4o/+1.570.5 weight ratio of methyl methacrylate/butyl acrylate/styrene/acrylic methacrylate. The material obtained by emulsion polymerization was used, which consisted of a total of five steps: a fourth step of polymerization, and a fifth step of polymerizing 15 parts by weight of a monomer mixture consisting of methyl methacrylate/methyl acrylate in a weight ratio of 11,871. Except for this, an injection molded product was obtained in exactly the same manner as in Example 1, and was evaluated according to the method performed in Example 1. The results are shown in Table 2.

As the rubber component (II), butyl acrylate/styrene/acrylic methacrylate 80/i11/1.
The first step is to polymerize 80 parts by weight of a monomer mixture consisting of a weight ratio of 80% by weight of methyl methacrylate/methyl acrylate.
a second stage of polymerizing 80 parts by weight of a monomer mixture consisting of a 9/1 weight ratio; a second stage of polymerizing 10 parts by weight of a monomer mixture consisting of a butyl acrylate/styrene/acrylic methacrylate weight ratio of 8071971.0; An injection molded product was obtained in exactly the same manner as in Example 1, except that the product obtained by emulsion polymerization consisting of three steps in total was used, and this was used as Example! The evaluation was carried out according to the method used in . The results are shown in Table 2.

As the rubber component (II), f of methyl methacrylate/methyl acrylate/1,3-butylene dimethacrylate
18/1. /20 of a monomer mixture consisting of a weight ratio of 1
The first stage of polymerizing 80 parts by weight of a monomer mixture consisting of 80/18/1.0/1.0 weight ratio of butyl acrylate/styrene/acrylic methacrylate/1,3-butylene dimethacrylate Second stage of polymerization, methyl methacrylate/methyl acrylate/1.3-
98.5 of butylene dimethacrylate. /1.010.
A third stage of polymerizing 10 parts by weight of a monomer mixture consisting of a weight ratio of 5 to 8 parts by weight of methyl methacrylate/methyl acrylate.
An injection molded product was prepared in exactly the same manner as in Example 1, except that a product obtained by emulsion polymerization consisting of a total of four stages, including the fourth stage of polymerizing 50 parts by weight of a monomer mixture having a weight ratio of 871. was obtained and evaluated according to the method performed in Example 1. The results are shown in Table 2.

6-14 and l-4 The methacrylic resin (I) used in Example 1 and the rubber component (1
An injection molded product was obtained in exactly the same manner as in Example 1, except that the amount of 1) and the amount of the type of compound (m) were changed as shown in Table 3. It was evaluated accordingly. The results are shown in Table 3.

As shown in Table 3, the intended purpose could not be achieved when the rubber component (■) was not added at all or when the amount of compound (m) added was outside the range of the present invention.

Procedural amendment January 28, 1985 Mr. Manabu Shiga, Commissioner of the Patent Office ■, Indication of the case, Patent Application No. 233704 of 1988 2, Name of the invention: Methacrylic resin composition 3, Person making the amendment Relationship to the case Patent Applicant name (803) Mitsubishi Rayon Co., Ltd. 4, Agent 5, Date of amendment order Page 17, line 10 of the invention specification booklet, page 18 of the same! 5th line, 2nd line
"Acrylic methacrylate" described on page O, line 7, line 10, line 13, line 18, page 21, line 7, line 12, and page 22, line 4, [ Allyl methacrylate” is corrected.

Claims (1)

[Scope of Claims] 1. 50 to 99.8% by weight of a methacrylic resin composed of 80% by weight or more of methyl methacrylate units and 20% by weight or less of other monomer units copolymerizable therewith; crosslinked acrylic Rubber component composed of acid ester copolymer 40~
0.1% by weight; the following formulas A, B, C. D, E, F, G and H: CH2-OR CH-OR, (A) CH20R2 CH2-0R3 R60CH7-C-CH2-OR, (B) CH7-OR
5 CH2-OR7 R90CH2-C-CH2-CH3 (C) Blind CH2-0R8 R. CH2CHOH R□. CON (D) CH2CHOH R. 14 CH2CHOH R,N (E) CH2CHOH ■ Is 0 0M Ru O(CH2CH20)n P (F)OM. R,, OP (G) 0M3 P-0M4 (H) R, TS O (In these formulas, R, R+, R2, R3, R, l. R5+ R6+ R7+ Re and R9 are the same as each other hydrogen or an alkyl group having 8 to 20 carbon atoms, R□G + R17+ RI@ and R, may be the same or different, and may be
The alkyl group of Rl@*Ru + R11+ R
u + R14 and RIG may be the same or different and represent an alkyl group having 1-18 carbon atoms, M,,'
, P4+, M2, M3 and M4 may be the same or different and represent hydrogen, Na, K and Ll, and n represents a number from 1 to 50. ) at least one compound selected from the group of compounds 10 to 0.
A methacrylic resin composition containing as much as 1% by weight. 2. The methacrylic resin composition according to claim 1, wherein the rubber component composed of the crosslinked acrylic ester copolymer contains an elastomeric component containing 50% by weight or more of acrylic ester units.