JPS6259658A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent environmental stress cracking resistance and is freed from the problem of laminar peeling, consisting of a rubber-contg. styrene resin and a copolymer. CONSTITUTION:100pts.wt. fatty acid vinyl ester monomer (e.g., vinyl acetate) or mixture thereof with other copolymerizable monomer (e.g., ethylene) and 0.01-10pts.wt. bifunctional long-chain monomer of formula I [wherein R<1>, R<2>, R<6>, R<7> are each H, CH3; X is -(CH2)l(CHR<3>)m(CR<4>R<5>)n- and/or a group of formula II; l, m, n, x, y are each 0 or greater; lambda+m+n is 5 or greater; R<3>-R<5> are each alkyl, aryl, alkoxyl, hydroxyl; Y is -O-, -S-, -SO2-, -CH2-, alkylidene, alkylene] are copolymerized to obtain a copolymer having a solubility parameter of 8.4-9.8(cal/cc)<1/2>, a glass transition temp. of 20 deg.C or below and a gel content of 70wt% or below. 1-50pts.wt. said copolymer and 100pts.wt. rubber-contg. styrene resin (e.g., ABS resin) are melt-kneaded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention is directed to a thermoplastic resin composition that has excellent environmental stress resistance and improved laminar peelability.

[Conventional technology]

When rubber-containing styrenic resins come into contact with chemicals under stress, cracks occur and, in severe cases, breakage is observed. This phenomenon is called environmental stress cracking phenomenon.
It is well known that this phenomenon is significantly observed in chemicals that do not have high solubility in resins, such as alcohols, carboxylic acids, esters, alkanes, and alkenes.

Environmental stress cracking phenomenon is caused by the distortion that remains inside the molded product even when no external force is applied to the resin molded product.
This occurs due to release due to contact with chemicals, which places great restrictions on the applications of rubber-containing styrenic resins.
There is.

The V content of the rubber component and the molecular weight of the resin component are known as factors that affect the environmental stress of rubber-containing styrenic resins. Although increasing the molecular weight improves the environmentally stressed pillars, the effect was insufficient for practical use.

Recently, the present inventors have discovered that by mixing a fatty acid vinyl ester polymer with a rubber-containing styrenic resin, the environmental stress resistance of the rubber-containing styrenic resin can be dramatically improved (% - Publication No. 56-147841).

However, the composition of the invention is 13! Although the improvement effect of J-boundary stress-formed columns is remarkable, mica-like layered peeling phenomenon is sometimes observed in injection molded products, and improvements are required. The delamination phenomenon is noticeable in molded products injection molded under high shear rate conditions, and is noticeable near r-).

The delamination phenomenon occurs when the fatty acid vinyl ester-based composite particles dispersed in the rubber-containing styrene-based resin are flattened due to the stress 9 during injection molding. For the purpose of preventing flattening of the fatty acid vinyl ester rice-produced combined particles, it is effective to copolymerize a polyfunctional vinyl monomer during polymerization of the fatty acid vinyl ester polymer.

[Problem that the invention seeks to solve]

However, for fatty acid vinyl ester polymers obtained by copolymerizing polyfunctional vinyl monomers such as divinylbenzene and ethylene glycol dimethacrylate,
Although the delamination phenomenon has been improved, the glue content is high and the effect of improving the environmentally stressed pillars of the rubber-functionalized styrene resin is insufficient. For this reason, by using a polyfunctional vinyl monomer and a chain transfer agent in combination to produce a fatty acid vinyl ester polymer with a low content and a branched structure, the layered structure becomes Although it is possible to measure the balance of soil-resistant and stress-resistant columns, the results are unsatisfactory in practical terms.

An object of the present invention is to provide a thermoplastic resin composition that improves the drawbacks of the prior art described above.

[Means for solving problems]

To summarize the present invention, the present invention relates to a thermoplastic resin composition, comprising: (A) a rubber-containing styrenic resin;
B) A thermoplastic resin composition containing 1 to 50 parts by weight of component (B) per 100 parts by weight of component (A), wherein the copolymer of component Φ is To 100 parts of a fatty acid vinyl ester monomer or a mixture of a fatty acid vinyl ester monomer and another copolymerizable monomer,
The following general formula I: [wherein R1 and R2 are H or cEI3 groups, X is -(CH2)t(CnH2)m(CR'R5JB
- group (t, m and n are integers of 660 or more, and L
10m+n is an integer of 5 or more, and R3, R
' and R5 are alkyl, aryl, alkoxyl or hydroxyl groups) and/or (X and y are integers of 640 or more, R6 and R7 are H or CH3 group thea'), /Y is -0 -1-8-1-8
O2-, -CH2-, alkylidene group or alkyl
: is a ren group)] □ A long-chain bifunctional monomer represented by 0.01 to 10 parts by weight of a monomer with a solubility parameter of 8.4 to 9.8 (Ca4
/cC)4, and the glass transition temperature is 20°C or less.
It is characterized by being a copolymer having a 1F' content of 70 points or less.

The resin composition of the present invention is excellent in 1 tffl boundary stress and is less likely to cause one-dimensional peeling phenomenon.

Monomers constituting the rubber component of the rubber-containing styrenic resin, which is component (A) in the present invention, include butadiene,
Conjugated diene monomers such as imprene, trimethylbutadiene, chloroprene, and cyclopentadiene, non-conjugated diene monomers such as 2.5-norpornathiene, 1#4-cyclohexadiene, and 4-ethylidene norbornene, styrene, α - Styrenic monomers such as methylstyrene and vinyltoluene; nitrile monomers such as acrylonitrile and methacrylonitrile; , olefin monomers such as ethylene, propylene, 1-butene, imbutylene, and 2-butene, and homopolymerization or copolymerization of these monomers are used.Also, crosslinking monomers such as ℃ polyfunctional vinyl A copolymer obtained by copolymerizing monomers can also be used, but the temperature is divinylbenzene, ethylene glycol dimethacrylate, 1°C, 6-butylene glycol dimethacrylate, 1°C. Examples include 4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, cyanuric triallyl, incyanurate triallyl, trimethylolpropane trimethacrylate, allyl acrylate, allyl methacrylate, vinyl acrylate, vinyl methacrylate, glycidyl acrylate, glycidyl methacrylate.

The rubber component used as component (A) of the present invention needs to have a graft active site, and specifically preferably has a carbon-carbon two X bond in the rubber molecule.

There are no particular restrictions on the method of polymerizing the monomers, including emulsion polymerization,
Known techniques such as solution polymerization can be used.

Also, the two components of component (A) do not need to be of one type,
It may be a mixture of two or more rubber components that are separately polymerized.

The monomers constituting the resin component of the rubber-containing styrenic resin, which is component (A) in the present invention, include styrene, α
- Styrenic monomers such as methylstyrene, vinyltoluene, and t-glylstyrene; nitrile monomers such as acrylonitrile and methacrylonitrile; Acid ester monomer, maleimide, N-methylmaleimide, N-ethylmaleimide, xi-f?/L
/maleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-)ruylmaleimide, N-xylylmaleimide, and other maleimide monomers.
It is used alone or as a copolymer at ℃, but it requires a styrene monomer.

The component (A) used in the present invention is composed of a rubber component and a resin component as described above, and a graft structure is present at the interface between the rubber component, which has a spherical structure, and the resin component, which is a continuous phase. is necessary. It is known that such a five-dimensional structure can be achieved by the so-called graft method, in which part or all of the monomers constituting the resin component are polymerized in the presence of a rubber component. The ingredients are also made using known graft polymerization technology! A can be built.

In order to determine the V content of the rubber component contained in component (A), it is possible to mix a separately polymerized resin component with component (A), but it is also possible to mix a separately polymerized resin component with component (A). The components do not need to have the same composition as the resin component obtained by graft polymerization. For example, a resin component obtained by copolymerizing acrylonitrile, styrene, and α-methylstyrene can be mixed with the obtained component (A) by grafting acrylonitrile, styrene, and methyl methacrylate in the presence of polybutadiene. .

Specific examples of component (A) of the present invention include high-impact polystyrene, ABS (acrylonitrile-butadiene-styrene resin), heat-resistant ABS (acrylonitrile-butadiene-styrene-α-methyfk styrene) resin, As (acrylonitrile-acrylic acid ester-styrene) 4ttjLAgs (acrylonitrile-BPD
Examples include M-styrene monomer MRAS (methyl methacrylate-citadiene-acrylonitrile-styrene) resin.

Next, examples of fatty acid vinyl ester monomers used as raw materials in the method for producing the copolymer which is component (5) of the present invention include vinyl ioate, vinyl acetate, vinyl propanoate, vinyl butanoate, Vinyl pentanoate, vinyl hexanoate, vinyl heptanoate, vinyl octoate, nona/
Examples include vinyl acid, vinyl decanoate, vinyl dodecanoate, vinyl tetradecanoate, vinyl hexadecanoate, vinyl octadecanoate, and the like.

On the other hand, ψU of other copolymerizable monomers is ethylene,
Olefin it forms such as phlopylene, 1-7'tene, 2-butene, imbutylene, cyclopentene, cyclohexene, norbornene, styrene, α-methylsteref,
t-f Styrenic monomers such as methyl styrene and P-methyl styrene, methyl acrylate, ethyl acrylate, butyl ac IJL/-), hexyl acrylate, cyclohexyl acrylate, octyl acrylate, hydroxyethyl acrylate, methoxyethyl acrylate, phenyl acrylate, glycidyl Acrylic acid ester monomers such as acrylate, methacrylic plate ester monomers such as methyl methacrylate, butyl methacrylate, glycizol methacrylate, nitrile monomers such as acrylonitrile, methacrylaterile, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, phenyl vinyl ether Examples include vinyl ether monomers such as Nato, halodanated olefin monomers such as vinyl chloride and vinylidene chloride.

In addition, component (B) of the present invention requires copolymerization of a long chain difunctional monomer, where the long chain difunctional monomer is represented by the general formula I [general Formula l] [In the formula, R1 and R2 are H or CH3 group, X is -(CH2
)z(CHR")m(CR'R'JB- group (t, m, and n are integers of 0 or more, and!, +m 10n is an integer of 5 or more, and R3, R4, and R5 are furkyl group, aryl!L alkoxyl group or hydroxyl group) and/or (X and y are frequencies of 640 or more, R' and R7 are H or CH3 groups, /Y is ~0-l- 8-1-BO
2-1-CH2-, an alkylidene group or an alkylene group] Specific examples of X include -C1(2-CH, -CI(, -CI(
2-0) i, -1 田3 ``0%- 2 what 2CH2 what 2-5-ah2-cu2-
a+, -ca2-cmin-1CH -C) (2-CH2-CH2-CH2-CH2-CH2
-CE(2-CH2, -CH2-CH, -CH2-CH
2-CH, -CH2-C) (2-CH2-CI(2-C
H2-2-CH, -CH2-CH2-CH2-an-C
H2-1CH2CH3, etc., and specific examples of compounds represented by the general formula I include H3 j a(, tx2-o-C-C=CH2, etc.).

These long-chain bifunctional monomers may be used alone, or two or more of them may be mixed and used at °C.

The use of the long chain bifunctional monomer is as follows: -CO, 01 to 10 parts per 100 parts of the monomer to be copolymerized as described above, and 0.01 to 7 parts of the monomer to be copolymerized. Particularly preferred. However, if the tray is less than 0.01 parts by weight, the effect of N-like peelability is poor, while if it exceeds 10 parts by weight, the effect is saturated.

Moreover, in addition to the long-chain bifunctional monomer, other polyfunctional vinyl monomers may be copolymerized in the component CB) in the present invention. Examples of usable polyfunctional hinyl It forms include divinylbenzene, ethylene glycol dimethacrylate, 1.5-butylene glycol dimethacrylate, 1.4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, triallyl cyanurate, Triallyl incyanurate, trimethylolpropane trimethacrylate, allyl acrylic L/-
), allyl methacrylate, vinyl acrylate, vinyl methacrylate, etc.

(The same component of the present invention is 8.4 to 9.F3 (cat/c
It is necessary to have a solubility parameter of 8.6 to 9.6 (cat/cC
Man “C” i, > le.

The solubility parameter referred to in this specification is based on the Polymer Handbook, 2nd edition, edited by Brandrup (J) and Immergut (LH), published by John Wiley Endossance Co., New York City, 1975. ~ff- Using the solubility parameter values listed on page 9 of 359, the solubility parameter δ of the copolymer.

, the solubility parameter δn of the individual vinyl monomer homopolymer constituting the copolymer consisting of vinyl monomers of the mwi group, and its! Quantity fraction W. It is calculated using the following formula H.

For example, the solubility parameters of polybutyl acrylate and polyethyl acrylate are 8.8 (cat/C
C) "A, 9.4 (Based on cat/CC, the solubility parameter of a copolymer consisting of polybutyl acrylate, 70 weight units, and polyethyl acrylate, 30 weight units, is 9.
．． Total US is 0(ca4/CC)s.

When the solubility parameter of the component (2) is less than 8.4 or more than 9.8, the environmental stress resistance of the resin composition of the present invention becomes low, which is not preferable.

It is necessary that the component of the present invention has a glass transition temperature of 20°C or lower, preferably 10°C or lower. If the glass transition temperature exceeds 20°C, the environmental stress resistance of the resin composition of the present invention becomes undesirable.

Furthermore, the glue component of the present invention must have a ker9 content of 70 points or less. In this specification, the glue content refers to the Φ component expressed as 1. Place the treetop pestle in a basket made of 400 mesh stainless steel wire mesh.
After leaving &&L in toluene at 5℃ for 24 hours, remove the charge and air-dry it in a hot water bath.(b) Measure the weight of each component (j9), and then use the following formula (■). "C" refers to the calculated value.

[B component small floor proboscis base) / 'I, l X I Q I
If the glue content of the component J (melon) exceeds 70'', the environmental stress resistance of the resin composition of the present invention will deteriorate, which is not preferable.

Although there are no particular limitations on the method of polymerizing component (B) of the present invention, production by emulsion polymerization is industrially most advantageous, and known techniques related to emulsion polymerization can be applied as desired.

In the present invention, (A) component toox Sumire and (B) component 1 to
However, if the content of the component is less than 1 part, the effect of improving the environmentally stressed column will be insufficient; If you exceed it, the effect will not be saturated, but the rigidity will decrease or become thicker.
! fl L <No.

In order to mix the body component and the middle nine components in the present invention,
By applying a known mixing technique, both components in an emulsified state, a particulate state, or a melting state are blended and melted and kneaded.
Therefore, the desired mixture can be easily obtained. The concerned (
When component 131 is produced by an emulsion polymerization method, the polymer latex is blended with component (A) in an emulsified state, particulate state, or molten state, and melt-kneaded at °C during the dehydration step or at the same time as the dehydration step. be able to. Among the bath melt kneading devices, there are bumper mixers, intensive mixers, mix routers, coneaters, extruders, rolls, and the like. In addition, the manufacturing method disclosed in JP-A No. 56-161656 can also be applied.Furthermore, in the present invention, additives other than the above, such as pigments, dyes, stabilizers, dispersants, reinforcing materials, It is also possible to add photochromic agents, lubricants, etc.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to embodiments and reference example 9, but the present EjA is not limited to these examples.

In addition, all parts and parts written below are based on the weighted i standard.

Reference 911 (A) Preparation of component (υ Mu-1, A-2, Mu-3% In the presence of the rubber latex shown in A to 5-1, add the corresponding monomer and perform emulsion polymerization method. Manufactured by.

(2) A-4 A toluene solution of EPDM rubber was mixed with the monomers shown in Table 1≦force u, and produced by a bath liquid polymerization method.

(3) A-6, A-7, A-8 Reference Example 2 of manufacturing by emulsion polymerization method of monomers shown in Table IVC
(B) Preparation of Components 100 parts of pure water, 4 parts of partially saponified polyvinyl alcohol, 0.1 part of potassium persulfate, and 0.2 parts of sodium acetate were added to a pressure-resistant autoclave, and after the contents were sufficiently replaced with nitrogen, Table 2 The entire amount of ethylene corresponding to the composition shown in was injected under pressure. After the contents were heated to 60°C, the entire amount of the monomers having the compositions shown in Table 2 except for ethylene was continuously added in the shade for 10 hours.

The combined weight of the initial press-in ethylene and the base, excluding the continuously added ethylene, was 100 parts.

After the addition was complete, stir at 70°C for another 5 hours to polymerize.
lt has finished.

Table 3 shows the properties of the obtained component (B).

The abbreviations of the long-chain bifunctional monomers used in Table 2 are as follows: H3 +0=CH2 fi3 +cck12 Further, the physical property values were determined by the following method.

(υ glass transition temperature) The component latex was pressed into an aqueous calcium chloride solution, the solid obtained at °C was dried, and the temperature was measured using DuPont type measuring instruments, 910 differential scanning calorimeter and 990 thermal analyzer.

(2) Solubility parameter The solubility Nf parameter value C unit of each polymer used to calculate the solubility parameter in each column is (ca4/Cc)W
J is as follows.

Polybutyl acrylate: 8.8 Polyethylene 28.1 Polyvinyl acetate = 9.4 Polyvinyl dodecanoate 28.8 Polyacrylonitrile: 12.5 (3) Glue content) Component latex 'a-, 4M calcium chloride The solid obtained by pressurizing into an aqueous solution at °C was dried. 1.0 g of it was accurately weighed, treated and measured as described above, and calculated according to formula (2).

Table 6 Example 1 and Comparative Example 1 ff1 80 parts of (A-1) latex (as a polymer) and 20 parts of Table 2 (B) component latex (as a polymer) were mixed in a latex state, and a calcium chloride aqueous solution was heated under pressure. After the addition, the mixture was stirred at 95°C, and the resulting precipitate was filtered to recover the polymer. After drying the resulting mixture, 40 parts of the mixture was added to Table 1 (60 parts of A-6,1 powder).
4.4'-Impropylidene-bis[monophenyl-so-furkyl (C12-C,) phosphite]
Manufactured by Adeka Argus Chemical (To), Mark (MARx) 1
Mix with 0.6 parts of 500J (hereinafter abbreviated as stabilizer) using a Henschel mixer, and mix with VC manufactured by Chuo Kishu Seisakusho Co., Ltd.
-40 (single screw extruder with pent) to obtain pellets.

The obtained pellets were used to make C molded products and the C physical properties were evaluated, and the results are shown in Table 4, Experiment Nos. 1 to 19.

In addition, the physical property measurement values of each column were determined by the following method.

tlJ Tensile yield point・・・・・・ASTM
D-638 (2) Izotsu impact strength...
...AI9TM D-256 (3j# chemical resistant (fracture resistant stress-clad column) ASTM D-638 Type I dumbbell was given 50 degrees of deflection, fixed to a jig, and coated with ethylene glycol monoether ether. , the time required to break when left at a temperature of 26°C in minutes.6UO in the table is 300
Indicates that no breakage occurs after 30 minutes.

(A) Layered Peelability Using a 5-ounce injection molding machine, a 50 x 20 x 2 plate-shaped product with a gate size of 5 x 3 x 1 m was molded. In Example 3 and Comparative Example 6 (experiment numbers 29 to 69) described below, the resin temperature? In other actual examples and comparative examples, the resin temperature was 200°C, and the injection speed was 90 mz/see.
The temperature of Venus was set at 40"C.

The layered peelability of the r-1 portion of the molded product was evaluated as follows in comparison with a standard sample. This indicates that AB is located between A rank and B7 rank.

A: No peeling at all B: Slight peeling C: Slight peeling Numbers 1 to 16 are 11 actual examples, and numbers 14 to 19 are comparative examples. As is clear from the ratio example, are the glass transition temperature, gel content, and dissolution antiparameter of component 0 within the range of the present invention? If it deviates from this, the column will have poor environmental stress resistance, and if the amount of long-chain bifunctional monomer used is too light, a delamination phenomenon will occur.

Example 2 and Comparative Example 2 In actual mtui, component (B) and L"C Table 2CB-3)'a
- The same procedure as in Example 1 was carried out except that the mixing ratio of (A-1) and (B-3) and the blending ratio of (Mu-6) powder were changed as shown in Section 5. Obtained pellets. Table 5 shows the results of making molded products from the obtained pellets and evaluating their physical properties.
It was shown to.

As is clear from Table 5, if the amount of addition of component (B) is insufficient, the column with +fil soil stress will be poor, and if it is too much, the rigidity will be poor and it will not be practical.

Implementation I6 and Comparative Example 6 Clothing 1 (A-1) latex and component latex,
Table 1 <, A-7) Latex or (A-8) Latex was mixed in a latex state, and after pressurizing a calcium chloride water bath solution, it was stirred at 105 to 120'C. The obtained precipitate was passed through, the -CN compound was recovered, and after drying, Aif! was added to 100 parts of the mixture. 3 parts of the stabilizer ';

A molded article was prepared using Samurare Yaku Red, and its physical properties were evaluated, and the results are shown in Table 6.

From Table 6, if (A-7) 6 or (A-8) is used for about 7 tricks from January to 7 to ζ, Do not copolymerize long chain difunctional monomers due to high shear stress during injection molding (J3)
When using this component, a remarkable delamination phenomenon is observed (
(65-67). However, with the ingredients of the present invention, little or no peeling phenomenon was observed, demonstrating the effects of the present invention (Croat 6 Experiment No. 29~
34).

After mixing the actual JM Reli 4 and Comparative Example 4 21 component powder with Table 2 (8 parts of E-3J latex (polymer 'C) and 0.6 parts of stabilizer in a Henschel mixer, Toshiba Machine Co., Ltd. -5Q(
The pellets were fed into a co-rotating twin-screw kneading extruder) to obtain pellets.

A molded article was made from the obtained pellets and its physical properties were evaluated, and the results are shown in Table 7.

It can be seen that the effects of the present invention are exhibited regardless of the type of rubber of component (A).

〔Effect of the invention〕

As explained above, in the thermoplastic resin composition of the present invention,
The molded product exhibits a remarkable infancy in that the layered peeling phenomenon does not easily occur, and it also exhibits the effect of being immersed in an environmental stress-resistant coating.

Claims (1)

[Scope of Claims] 1 (A) includes a rubber-containing styrene resin and (B) a copolymer, and contains 1 to 50 parts by weight of the (B) component per 100 parts by weight of the (A) component. In the thermoplastic resin composition, the copolymer of component (B) is added to 100 parts by weight of a fatty acid vinyl ester monomer or a mixture of a fatty acid vinyl ester monomer and another copolymerizable monomer, General formula below
I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] [In the formula, R^1 and R^2 are H or CH_3 groups, and X is -(
CH_2)_l(CHR^3)_m(CR^4R^5)
__n- group (l, m, and n are each integers of 0 or more, and l+m+n is an integer of 5 or more, R^3, R^4, and R^5 are alkyl groups, aryl groups, alkoxyl groups, or is a hydroxyl group) and/or ▲ has a mathematical formula, chemical formula, table, etc. ▼ group (x and y are each an integer of 0 or more, R^6 and R^
7 is H or CH_3 group, Y is -O-, -S-, -
SO_2-, -CH_2-, alkylidene group or alkylene group) is obtained by copolymerizing 0.01 to 10 parts by weight of a long chain bifunctional monomer, and the solubility parameter is 8. 4-9.8 (cal/CC) ^
1^/^2, a glass transition temperature of 20°C or less, and a gel content of 70% by weight or less.