JPH04122758A - Vinyl chloride-n-substituted maleimide copolymer composition - Google Patents

Abstract

PURPOSE:To prevent initial coloration and improve the transparency of a molded item by compounding a specific vinyl chloride-N-substd. maleimide copolymer with an alkyltinmercaptocarboxylic ester and an alkyltin chloride. CONSTITUTION:A vinyl chloride-N-substd. maleimide copolymer having a viscosity average mol. wt. of 300-3000 is prepd. by copolymerizing 55-99wt.% vinyl chloride, 1-50wt.% N-substd. maleimide of formula I [wherein R<1> and R<2> are each H or 1-3C alkyl; and R<3> is a 1-30C (substd.) aliph., arom., or alicyclic group], and if necessary, 20wt.% other monomer or other polymer onto which vinyl chloride and the maleimide can be grafred. 100 pts.wt. said copolymer is compounded with 0.05-5 pts.wt. alkyltinmercaptocarboxylic ester selected from the group consisting of comps. of formulas II and III (wherein R<4> and R<5> are each 1-18C alkyl; R<6>, R<7>, and R<8> are each R<4> or 1-4C alkoxyalkyl; and (n) is 1 or 2) and 0.05-5 pts.wt. alkyltin chloride selected from the group consisting of compds. of formulas IV to VIII.

Description

[Detailed Description of the Invention] [Industrial Application Field] This invention particularly relates to vinyl chloride with improved initial colorability.
The present invention relates to an N-substituted maleimide copolymer composition.

[Conventional technology]

Vinyl chloride-N-i! Below, V
C-Ml) retains the advantages of vinyl chloride resin, such as flame retardancy, water resistance, chemical resistance, and weather resistance, and has an improved heat distortion temperature. Therefore, it is expected to be used in applications that require heat resistance, such as electronic component cases, display boards, and nameplates.

However, when VC-MI is heated and melt-molded, it tends to discolor to yellow or brown, and its appearance is not satisfactory for the above-mentioned uses.

Therefore, in order to improve the heat and stability of VC-Ml, for example, Japanese Patent Application Laid-Open No. 63-309549 discloses that VC-Ml
A composition has been proposed in which a methyltin mercapto stabilizer is added to 1.

[Problem to be solved by the invention]

However, V containing the above-mentioned methyltin mercapto stabilizer
Although the C-M1 composition had excellent long-term thermal stability, it was insufficient to eliminate initial coloration.

In view of the above-mentioned problems, it is an object of the present invention to provide a VC-M1 composition that eliminates the initial coloring property and can be molded into a transparent molded product.

[Means to solve the problem]

This inventor discovered that by adding to VC-MI a specific alkyltin mercaptocarboxylic acid ester described later and a specific alkyltin chloride described below in combination, or further containing a specific mercaptocarboxylic acid ester described below. , succeeded in eliminating the initial coloration.

In the VC-MI of this invention, the N-substituted maleimide copolymerized with the vinyl chloride monomer includes, for example, N-
Methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide, N-1s.

-Propylmaleimide, N-n-butylmaleimide, N
-t-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, NO-hydroxymaleimide, N-m-hydroxymaleimide, N-p-hydroxymaleimide, and the like. One or more of these may be used.

In this VC-Ml, the N-W exchanged maleimide is 1
If it is less than % by weight, the improvement in heat distortion temperature is insufficient;
On the other hand, if it exceeds 50% by weight, the molding processability will be extremely reduced, so the content should be 1 to 50% by weight. Preferably it is 5 to 40% by weight, more preferably 10 to 30% by weight.

In addition, the polymerization method of this VC-MI includes bulk polymerization method,
Any method such as a suspension polymerization method, a solution polymerization method, an emulsion polymerization method, etc. may be used, but the suspension method is usually most advantageously employed from the viewpoint of economy and quality.

Further, during the polymerization of VC-MI, other monomers and other polymers to which the vinyl chloride monomer can be graft-polymerized may be used together, if necessary.

For example, other monomers include ethylene, propylene,
Olefinic monomers such as butylene, vinyl ester monomers such as vinyl acetate and vinyl stearate, alkyl vinyl ether monomers such as isobutyl vinyl ether and cetyl vinyl ether, halogenated monomers such as hnylidene chloride, vinyl fluoride, and vinyl bromide. Olefin monomer, ethyl (meth)acrylate, n-butyl (meth)acrylate,
(meth)acrylic acid ester monomers such as 2-ethylhexyl (meth)acrylate and stearyl (meth)acrylate, and these monomers may be used alone or in combination of two or more.

Other polymers that can be graft-polymerized with vinyl chloride monomers include ethylene-vinyl acetate copolymer, ethylene-methyl (meth)acrylate, and ethylene-ethylene (meth)acrylate.
Ethylene-(meth)acrylic ester copolymers such as meth)acrylate, ethylene-vinyl acetate-carbon oxide copolymers, ethylene-(meth)acrylic esters such as ethylene-methyl(meth)acrylate-carbon oxide, etc. Carbon oxide copolymers, polybutadiene-styrene-methyl methacrylate (MBS), MBS-based copolymers such as polybutadiene-α-methylstyrene-methyl methacrylate, polybutadiene-styrene-acrylonitrile,
ABS copolymers such as polybutadiene-α-methylstyrene-acrylonitrile, styrene-maleic anhydride copolymers, styrene-glutarimide copolymers, chlorinated polyethylene, polyurethane copolymers, acrylonitrile-α-methylstyrene, etc. As copolymer, styrene-
Examples include butadiene copolymer, polystyrene, chloroprene rubber, butyl rubber, etc., and these polymers may be used not only alone but also in combination of two or more.

The amount of these monomers or polymers used is such that it does not impair the performance of VC-MI, that is, preferably within 20% by weight, more preferably within 15% by weight of VC-MI.

The degree of polymerization of VC-Ml is not particularly limited, but if the viscosity average degree of polymerization is less than 300, the strength will be extremely reduced,
If it exceeds 3,000, the molding processability will be extremely deteriorated, so the viscosity average degree of polymerization is preferably 300 to 3,000, and 500 to 3,000.
It is particularly preferable that it is 2,000 to 2,000.

Furthermore, during the polymerization of VC-MI, vinyl chloride monomer and N-substituted maleimide may be added all at once into the polymerization vessel before the start of polymerization. According to this relationship, vinyl chloride monomer or N-substituted maleimide may be added sequentially into the polymerization vessel in order to cause a homogeneous reaction.

The alkyltin mercaptocarboxylic acid ester (a) used in this invention is a dialkyltin mercaptocarboxylic acid ester represented by the general formula [nl or the general formula [I[[
] It is a monoalkyltin mercaptocarboxylic acid ester represented by the following. Examples of the dialkyltin mercaptocarboxylic acid ester [I[] include dialkyltin (isooctylmercaptoacetate), dialkyltin bis(2-ethylhexylmercaptoacetate), dialkyltin bis(isooctylpropionate), dialkyltin Bis(methoxybutylmercaptopropionate)
Examples of the monoalkyltin mercaptocarboxylic acid ester [■] include monoalkyltin tris (isooctyl mercaptoacetate), monoalkyl tin tris (2-ethylhexyl mercaptoacetate), monoalkyl tin tris ( stearylmercaptoacetate), monoalkyltin tris(isooctylpropionate), monoalkyltintris(methoxybutylmercaptopropionate), and the like. and,
One or more of these alkyltin mercaptocarboxylic acid esters may be used.

Examples of the alkyltin chloride (c) used in the present invention include dialkyltin isooctylmercaptoacetate chloride represented by -a formula [IV], dialkyltin isooctylpropionate chloride,
Dialkyltin methoxybutyl mercaptopropionate chloride, etc., dialkyltin dichloride represented by the general formula [V], monoalkyltin bis(isooctylmercaptoacetate) chloride represented by the general formula [VI], monoalkyltin Bis(stearylmercaptoacetate)・chloride, monoalkyltin bis(isooctylbouvionate)・chloride, monoalkyltin bis(methoxybutylmercaptopropionate)・
chloride etc., monoalkyltin isooctylmercaptoacetate dichloride, monoalkyltin stearylmercaptoacetate dichloride, monoalkyltin isooctylpropionate, represented by the general formula [■1]
Examples include dichloride, monoalkyltin methoxybutyl mercaptopropionate dichloride, and monoalkyltin trichloride represented by the general formula [■1]. One or more of these may be used.

Among these alkyltin chlorides, dialkyltin mercaptocarboxylic acid ester/chloride-based alkyltin chlorides, dialkyltin dichloride, and monoalkyltin mercaptocarboxylic acid ester/dichloride-based alkyltin chlorides are more suitable in terms of initial coloring property and processability. used for.

In the vinyl chloride-N-1 substituted maleimide copolymer composition of the present invention, if the amounts of the alkyltin mercapto and alkyltin chloride added are small, the thermal stability will decrease and the moldability will deteriorate. On the other hand, even if the amount is increased, the effect of improving initial colorability does not improve;
Since the heat distortion temperature decreases, VC-MI10
Each is added in an amount of 0.05 to 5 parts by weight relative to 0 parts by weight.

In the second aspect of the invention, a mercaptocarboxylic acid ester is further added to the vinyl chloride-N-substituted maleimide composition. Examples of the mercaptocarboxylic acid ester include mercaptoacetic acid methyl ester represented by the general formula [IX], mercaptoacetic acid 2-ethylhexyl ester, mercaptoacetic acid isooctyl ester, mercaptoacetic acid stearyl ester, mercaptopropionic acid inoctyl ester, etc. Ethylene glycol bis(mercaptoacetate) represented by the formula [X], 1.4
-Butanediol bis (mercaptoacetic acid ester), propylene glycol bis (mercaptopro and onic acid ester), and the like.

When the amount of the mercaptocarboxylic acid ester added is small, the effect of improving the initial coloring properties is small, and even when the amount is increased, the effect is not improved, but rather the heat distortion temperature is lowered. Therefore, 0.05 to 5 parts by weight are added to 1100 parts by weight of VC-M.

Furthermore, VC-M? In order to improve the moldability and mechanical strength of the composition, commonly used polyethylene waxes, higher fatty acids, higher alcohols, various ester-based lubricants, acrylic processing aids, ultraviolet absorbers, and fillers are used. ,
Of course, pigments, dyes, etc. may be added as appropriate.

Furthermore, if necessary, tin-based stabilizers other than the composition of the present invention, such as dialkyltin malate-based and dialkyltin laurate-based, calcium stearate, lead stearate, barium stearate, zinc stearate, barium stearate, and stearin. metal soap stabilizers such as magnesium acid, aluminum stearate, di-2-ethylhexyl phthalate, n-octyl phthalate, di-2-ethylhexyl separate, di-2-ethylhexyl adipate, tri-2-ethylhexyl trimeryl Reinforcement of tate, polyester-based plasticizers, trimethyl methacrylate-butadiene-styrene copolymer (MBS), ethylene-vinyl acetate copolymer, chlorinated polyolefin, acrylonitrile-butadiene-styrene copolymer, acrylic, etc. Agents may also be used together.

The vinyl chloride-N-substituted maleimide composition of this invention comprises:
Extrusion molding, calendar molding, blow molding, press molding,
A molded article is produced by appropriately employing a molding method conventionally used for molding thermoplastic resins, such as injection molding.

〔Example〕

The present invention will be explained in detail below. Note that parts refer to parts by weight.

MBS resin (manufactured by Mitsubishi Rayon Co., Ltd.; Metablen C
-110) 10 parts, polyethylene wax (Mitsui Petrochemical Industries, Ltd.; Hiwax 4202G) 0.5 parts, stearic acid (Yoken Fine Chemicals; F-3) 0.5 parts
The resin composition prepared by adding the following parts was thoroughly mixed, roll-kneaded at 185°C for 3 minutes, and then pressed at 180°C for 7 minutes to obtain a sheet with a thickness of 1 mm.

1st Order 1 1st Shift 2 3 in Table 1 Note) Ai Vinyl chloride-cyclohexylmaleimide copolymer (weight ratio 90:10) B: Vinyl chloride-cyclohexylmaleimide copolymer (weight ratio 70: 30) C: Vinyl chloride-phenylmaleimide copolymer (weight ratio 90
:10) The initial colorability of the obtained sheet was measured by the difference in yellowness ΔYl from a standard white board using a formula difference meter (manufactured by Nippon Heavy Industries Co., Ltd.).

As shown in Table 1, the composition of the present invention had low yellowing and excellent transparency.

(Effects of the Invention) As described above, the vinyl chloride-N-fi-converted mamarimide copolymer composition of the present invention contains a specific alkyltin mercaptocarboxylic acid ester and a specific alkyltin chloride in VC-MI. Furthermore, by containing a specific mercaptocarboxylic acid ester, initial coloring can be eliminated, making it suitable for applications that require heat resistance, such as electronic component cases, display boards,
It is expected that it will be used for nameplates, etc.

Claims (1)

[Claims] 1. 55 to 99% by weight of vinyl chloride monomer and a compound of the general formula [
100 parts by weight of vinyl chloride-N-substituted maleimide copolymer consisting of 1 to 50% by weight of N-substituted maleimide represented by ▲numerical formulas, chemical formulas, tables, etc.▼・・・・・・［I
] (a) 0.05 to 5 parts by weight of one or more selected from the group consisting of alkyltin mercaptocarboxylic acid esters represented by general formulas [II] and [III], ▲ mathematical formula, chemical formula , tables, etc.▼・・・・・・［II］ ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・［III
] (b) General formulas [IV], [V], [VI], [VII] and [
0.05 to 5 parts by weight of one or more selected from the group consisting of alkyltin chlorides represented by ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[V] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・［VI] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・...[VII
] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・［VII
I] A vinyl chloride-N-substituted maleimide copolymer composition characterized by containing the following. However, in the formula, R^1 and R^2 represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and R^3 represents a substituted or unsubstituted aliphatic, aromatic, or alicyclic group having 1 to 30 carbon atoms. Indicates a group, R^4
and R^5 represents an alkyl group having 1 to 18 carbon atoms, R^
6, R^7 and R^8 represent an alkyl group having 1 to 18 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms, and n is 1
or 2. 2. (d) Contains 0.01 to 5 parts by weight of one or more selected from the group consisting of mercaptocarboxylic acid esters represented by general formulas [IX] and [X]. 2. The vinyl chloride-N-substituted maleimide copolymer composition according to claim 1. HS(CH_2)_nCOOR^6...[IX]
HS(CH_2)_nCOOXOOC(CH_2)_n
SH・・・・・・[X] However, in the formula, R^6 is a carbon number of 1 to
18 alkyl group or an alkoxyalkyl group having 1 to 4 carbon atoms, X represents an alkylene group, and n represents 1 or 2.