JPS61258856A - Low-temperature impact-resistant resin composition having improved coloring property and thermal decomposition resistance - Google Patents

Abstract

PURPOSE:A composition having improved coloring properties, thermal decomposition resistance and low-temperature impact resistance, obtained by blending a non-diene rubber reinforced resin and a graft polymer with a compound having a specific phenolic structure and an ester bond. CONSTITUTION:100pts.wt. composition consisting of (A) a non-diene rubber reinforced resin and (B) a graft polymer obtained by polymerizing an unsaturated carboxylic acid alkyl ester compound or it and another polymerizable compound in the presence of a diene rubber-like polymer (a composition ratio of the component A to B of preferably 20-80wt%:80-20wt%) is blended with (C) 0.01-5pts.wt. compound having a phenolic structure and an ester bond in the molecule. A monomer ester shown by the formula (R is 1-4C alkyl) of acrylic acid and 2,2'-methylene-bis-(4-alkyl-6-t-butylphenol) where R is especially methyl is used as the component C.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a 5t low-temperature tube with excellent color development and thermal decomposition resistance.
-Relating to an injection resin composition.

[Conventional technology]

Graft polymers obtained by polymerizing ethylene-propylene rubber, which is a non-diene rubber, with aromatic vinyl compounds, vinyl cyanide compounds, etc. AES resin, which is a mixture with a polymer, has excellent weather resistance, impact resistance, and chemical resistance, and is expected to be used in a wide range of fields, but it has poor coloring properties and cannot be colored in vivid colors. Therefore, it has already been proposed that a composition with excellent coloring properties can be obtained by blending polymethyl methacrylate (PMMA) with AES resin. (% Kaisho 5
7-117557 and JP-A-57-139139) Furthermore, a kraft polymer obtained by polymerizing a compound mainly composed of methyl methacrylate in the presence of an alkyl acrylate (co)polymer or a diene rubber polymer instead of PMMAK. It has also been proposed that a composition in which reduction in impact resistance is prevented can be obtained by incorporating a coalescent. (JP-A-57-164147, JP-A-59-1) [Means for Solving the Invention] However, PMMA or the graft polymer as described above is blended into the 7' (AES resin composition). Poor thermal decomposition resistance during molding, especially when retained in a molding machine.

[Means for solving problems]

As a result of intensive research aimed at solving these drawbacks, the present inventors have found that a composition consisting of an AES resin composition blended with a graft polymer and a certain percentage of a compound has improved color development, heat decomposition resistance, and low temperature cylinder performance. The present invention was achieved by discovering that it has excellent moldability.

That is, the present invention provides a graft polymer obtained by polymerizing an unsaturated carboxylic acid alkyl ester compound or this and other polymerizable compounds in the presence of a non-diene rubber reinforced resin (A) and a diene rubber polymer. 0.01 to 5 parts by weight of a compound (Q) having a phenol structure and an ester bond in the molecule per 100 parts by weight of the composition consisting of the combination (B). The object of the present invention is to provide a low-temperature cylindrical resin composition with excellent properties.

The present invention will be explained in more detail.〇〇Non-diene rubber reinforced resin (A) The non-diene rubber reinforced resin (A) used in the present invention is an aromatic vinyl compound, cyanide, etc. in the presence of a non-diene rubber. A graft polymer (a) obtained by polymerizing one or more compounds selected from at least two groups of vinyl chloride compounds and other polymerizable compounds, or a graft polymer (a) obtained by polymerizing this with an aromatic vinyl compound, a vinyl cyanide compound, and others. each one selected from at least two groups among the polymerizable compounds of
This is a resin composition consisting of a copolymer (b) obtained by polymerizing more than one type of compound.

Examples of the non-diene rubber constituting the graft polymer (a) used in the present invention include ethylene-prolene-propylene-nonconjugated diene copolymer, ethylene-vinyl acetate copolymer, and acrylic rubber such as polybutyl acrylate. Examples include acid alkyl ester polymers, chlorinated polyethylene, etc., and one or more types can be used. Especially ethylene-propylene copolymers and ethylene-
Propylene-nonconjugated diene copolymers are preferred.

The aromatic vinyl compounds constituting the non-diene rubber reinforced resin (kraft polymer (a) and copolymer (b)) include styrene, α-methylstyrene, α-chlorostyrene, P-methylstyrene, p- t-7' Chill Styreshi,
0-Chlorstyrene, p-chlorostyrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,5-
Examples include dibrom styrene, and one type or two or more types can be used. Styrene is particularly preferred.

Examples of vinyl cyanide compounds include acrylonitrile,
Examples include methacrylate trile, maleonitrile, fumaronitrile, etc., and one or more types can be used. Acrylonitrile is particularly preferred.

Other polymerizable compounds include unsaturated carboxylic acid alkyl ester compounds, such as methyl (meth)acrylate,
Ethyl (meth)acrylate, Propyl (meth)acrylate, Butyl (meth)acrylate, Lauryl (meth)acrylate, Cyclohexyl (meth)acrylate, (Meth)
Examples include 2-hydroxyethyl acrylate, glycidyl (meth)acrylate, dimethylamine ethyl (methacrylate), methyl maleate, ethyl maleate, butyl maleate, and one or more types can be used. Particularly Methyl methacrylate is preferred.

Non-diene rubber reinforced resin (The composition ratio of the non-diene rubber and the compound in No. 8 is not particularly limited, but it is preferably 5 to 80% by weight of the non-diene rubber and 95 to 20% by weight of the compound. In addition, there is no particular restriction on the composition ratio of each compound in the compound subjected to polymerization, but 25 to 85% by weight of the aromatic vinyl compound and 75 to 15% by weight of the cyanated vinylide metal and/or other polymerizable compound. It is preferable that

2 selected from such compounds in the presence of a non-diene rubber.
The graft polymer (a) obtained by polymerizing more than one type of compound can be obtained by a known polymerization method, such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, or a combination thereof.

In the copolymer (b), one or more compounds selected from at least two groups of aromatic vinyl compounds, vinyl cyanide compounds, and other polymerizable compounds are used. The weight ratio of these compounds is not particularly limited, but preferably 25 to 85 parts by weight of the aromatic vinyl compound and 75 to 15 parts by weight of the vinyl cyanide compound and/or other polymerizable compound.

Although the intrinsic viscosity (30° C., dimethylformamide) of the copolymer value is not particularly limited, it is preferably 0.40 to 1.10. Such copolymer (b) can be obtained by known polymerization methods, such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, and combinations thereof.

0 Graft Polymer (B) Graft Polymer (B) Examples of the diene rubbery polymer in K include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, etc., and one or more of them are used. be able to.

The unsaturated carboxylic acid alkyl ester f arsenic compounds constituting the graft polymer (B) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, ( Lauryl meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, dimethylamineethyl (meth)acrylate, methyl maleate, ethyl maleate , butyl maleate, etc. may be used alone or in combination.Methyl methacrylate is preferred in % bo. Examples of polymerizable compounds include styrene, α-methylstyrene, α-chlorostyrene, P-methylstyrene, p-t-methylstyrene, 0-chlorostyrene, p-chlorostyrene, 2
, 5-dichlorostyrene, 3,4-dichlorostyrene,
2) aromatic vinyl compounds such as 5-dibromustyrene;
Examples include acrylonitrile, methacrylonitrinopemaleonitrile, fumaronitrile natonocyaninated vinyl compounds, and the like. Styrene is particularly preferred.

It is a polymerizable compound of There is no particular restriction on the composition ratio of the diene-based rubbery polymer and the f-hybrid compound in ), but from the viewpoint of low-temperature cylindrical formability, coloring property, and weather resistance of the final composition, diene-based rubbery polymers 1 to 1 are used. 60% by weight, compound 99-40
Weight % is preferable, especially diene rubbery polymer 1 to 20
Weight percent is preferred.

Such graft polymer (B) can be obtained by known polymerization methods, such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, and combinations thereof.

Compound (C) having 0 phenol structure and ester bond
Compounds having a phenol structure and an ester bond in the molecule used in the present invention (q is propionic acid, carboxylic acid such as acrylic acid is a lower alkyl ester thereof, or its acid chloride and methylene bisphenol, phthylidene bisphenol, thiobisphenol, etc.) It is a compound produced by reacting bisphenols or their nuclear alkyl-substituted products by a known method.In particular, it has the general formula % (wherein R represents an alkyl group having 1 to 4 carbon atoms). Acrylic acid and 2,2-methylene-bis-(4-
monoester of 2-t-butyl-6-(3-t-
-butyl-5-alkyl-2-hydroxybenzyl)-
4-alkylphenyl acrylate is preferred. Also,
In the compound represented by the general formula, the substituent R is preferably a methyl group or an ethyl group, and a methyl group is particularly preferred. This composition contains 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight, of the compound (C) having a phenol structure and an ester bond per 100 parts by weight of the composition.

There is no particular restriction on the composition ratio of the non-diene rubber reinforced resin matrix and the graft polymer (B) in the resin composition; ) It is preferably 95 to 5% by weight. If the graft polymer (B) exceeds 95% by weight, the impact resistance at low temperatures will decrease, and the compatibility with non-diene rubber reinforced resin (N) will be poor, and the surface of the molded product will appear pearlescent. Therefore, it is not possible to obtain a resin composition with good color development and excellent low-temperature impact properties, which is the objective of the present invention.Furthermore, if the graft polymer CB) is less than 5 overlapped parts, layer peeling will occur, and insufficient color development will occur. The t problem is not solved at all, and clear coloring cannot be achieved.

In particular, 20 to 80% by weight of non-diene rubber reinforced resin (A)
, graft polymer (B) 80 to 20% by weight is preferred.

0 mixed non-diene rubber reinforced resin (4), graft polymer (B)
and compounds with a phenolic structure and an ester bond (
Examples of the mixing method in C) include a known mixing method using a Banbury mixer 1 extruder or the like.

In the present invention, known dyes and pigments can be used, and the composition of the present invention has excellent color development and heat decomposition resistance with any of the dyes and pigments. Particularly, when impurities in the dye and pigment promote decomposition of the resin composition, a special effect is exhibited.

When mixing, not only dyes and pigments but also known stabilizers, plasticizers,
It is also possible to add antistatic agents, ultraviolet absorbers, lubricants, fillers, etc.

EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these in any way.
' Examples and Comparative Examples Non-diene rubber reinforced resin (5) consisting of graft polymer (a) or its copolymer (b), graft polymer (
B) (or butyl acrylate graft polymer (b)
, PMMA) and a compound having a phenol structure and an ester bond (Q) were colored and kneaded in a Banbury mixer (200° C., 4 minutes) based on the compounding ratio shown in Table 1 to obtain various compositions.

Pigment formulation (per 100 parts by weight of resin composition) Red
: Cadmi Red 1.5 parts by weight Blue : Ultramarine $2000 0.3 parts by weight Black : Carbon 8
Using the obtained composition in an amount of 1.5 parts by weight, test pieces were prepared using an injection molding machine.

The molding conditions are as follows.

Molding Kiko Nippon Steel N-140A type injection molding machine (7
oz) Molding temperature: 250℃ Injection pressure 100kLi/Gauge Injection speed:
FCV8 Molding cycle = 1 minute (no retention) 10 minutes (with retention) Similarly, a colored resin composition was obtained using a commercially available ABS resin, "Talarastic M H'i" manufactured by Raw Kawara Naugatuck Co., Ltd., and for color development evaluation. standard.

The test results are shown in Table-1. In addition, for special orders other than color development,
All products are colored red.

<Non-diene rubber reinforced resin prisoner> Graft polymer (a-1) Ethylene-propylene-ethylidenenorbornene"EP
370 parts by weight of DM" (iodine value 8.0, Mooney viscosity 61, propylene content 43% by weight) was added to 30 parts by weight of n-hexane.
250 parts by weight of styrene, 130 parts by weight of acrylonitrile
67 parts by weight and 13 parts by weight of benzoyl peroxide were added.
Polymerization was carried out at 10° C. in a nitrogen atmosphere for 10 hours. The polymerization solution was brought into contact with a large excess of methanol, and the deposited precipitate was separated and dried to obtain a graft polymer (a-1).

Graft polymer (a-2) 450 parts by weight of water, 0.35 parts by weight of a suspending dispersant (hydroxyethyl cellulose), and ethylene-propylene-ethylidenenorporene ground to an average size of 3rIrM squares.
EP D M” (iodine value 8.5, Mooney viscosity 61,
Propylene content: 43 parts by weight) 100 parts by weight, 75 parts by weight of styrene, 40 parts by weight of acrylonitrile, and 2.3 parts by weight of t-butyl peroxide as an initiator,
After stirring at 26°C for 1 hour, the mixture was further heated to 110°C to carry out polymerization. Thereafter, the reaction product was cooled to room temperature, filtered and dried to obtain a graft polymer (a-2).

Graft polymer (a-3) Graft polymer (a-3) was obtained by replacing 75 parts by weight of styrene in graft polymer (a-2) with 35 parts by weight of styrene and 40 parts by weight of methyl methacrylate.
) was obtained.

Copolymer (b-1) 35 parts by weight of styrene and 30% by weight of acrylonitrile
Polymerization was carried out in an aqueous dispersion containing 100 parts by weight of a mixed solution of Kt-dodecylmercaptan, 0.1 parts by weight, and 0.3 parts by weight of benzoyl peroxide, by increasing the temperature from 30°C to 90°C for 10 hours. Copolymer with an intrinsic viscosity of 0.50 after dehydration (
b-1) was obtained.

Copolymer (b-2) 200 parts by weight of water with lauryl sulfate as an emulsifier) IJ
3.0 parts by weight of um, persulfate power IJ '7 as an initiator
After adding 0.4 parts by weight of A, α-methylstyrene 75
3 of a mixed monomer solution consisting of 25 parts by weight of acrylonitrile and 0.2 parts by weight of t-dodecylmercaptan.
0% was added, and polymerization was carried out at 65° C. for 1 hour in a nitrogen atmosphere. Furthermore, the remaining mixed monomers were continuously added for 3 hours to polymerize, and after aging at 70°C for 3 hours, salting out with aluminum sulfate,
After drying, a copolymer (b-2) having an intrinsic viscosity of 0.48 was obtained.

<Graft polymer B> 5 parts by weight of polybutadiene rubber and 8 parts by weight of methyl methacrylate
After dissolving in a mixed solution of 0 parts by weight and 15 parts by weight of styrene, the digraft polymer (
B) was obtained.

<Graft polymer b> A copolymer latex consisting of 80 parts by weight of butyl acrylate and 20 parts by weight of styrene was prepared, and 50 parts by weight of this copolymer latex (solid content) and 50 parts by weight of methyl methacrylate were emulsified and grafted. The graft polymer (b) was obtained by polymerization, salting out, dehydration, and drying.

<PMMA> Commercially available polymethyl methacrylate resin, manufactured by Igawara Kagaku Co., Ltd.
Specex B-LG".

<Compound (C) having a phenol structure and an ester bond
〉Acrylic acid and 2,2-methylene-bis(4-methyl-
2-t- which is a compound having a phenol structure and an ester bond obtained by reacting 6-t-butylphenol)
Butyl-6-(3!-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenylacrylate.

amount added to.

2) The color difference from ABS resin colored products is indicated by △E.

For Black Vc, the degree of jet blackness is determined by the naked eye.

3) Visually judge the degree of silver streaks that occurred on the injection molded test piece.

4) W〃 Measure the thickness and notched isot impact strength.

5) Koka formula 70-210℃, 30 kg/ctr
6) After 1000 hours of irradiation with a weatherometer, measure the thickness and unnotched Izot impact strength at -10°C, and calculate the retention rate by comparing it with the strength before irradiation. 7) After 1000 hours of irradiation with a weatherometer Measure gloss,
Retention rate calculated by comparing with gloss before irradiation.

<Effects of the Invention> A composition obtained by blending an ene-based rubbery polymer with a graft polymer obtained by polymerizing methyl methacrylate in the presence of a butyl acrylate polymer or PMMA (
Comparative Examples 2 to 4) are all inferior in heat decomposition resistance iK, and Comparative Examples 3 to 4 are also inferior in notched isot impact strength at low temperatures.

Compared to such conventional compositions, a composition consisting of a non-diene rubber reinforced resin and a carboxylic acid graft polymer obtained by polymerizing an unsaturated carboxylic acid alkyl ester compound in the presence of a diene rubber polymer. The composition of the present invention is formed by adding a small amount of a compound having a phenol structure and an ester bond to
It has excellent color development, thermal decomposition resistance, and low-temperature cylindrical shape.

Claims (1)

[Scope of Claims] 1) Obtained by polymerizing an unsaturated carboxylic acid alkyl ester compound or this and another polymerizable compound in the presence of a non-diene rubber reinforced resin (A) and a diene rubber polymer. A coloring property characterized by containing 0.01 to 5 parts by weight of a compound (C) having a phenol structure and an ester bond in the molecule per 100 parts by weight of a composition comprising the graft polymer (B); A low-temperature impact resin composition with excellent thermal decomposition resistance. 2) Compound (C) is a combination of acrylic acid and 2,2'-methylene- represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents an alkyl group having 1 to 4 carbon atoms.) Bis(
The low-temperature impact resin composition according to claim 1, which is a monoester (4-alkyl-6-t-butylphenol).