JPH08208932A - Heat resistant vinyl chloride resin composition - Google Patents

Abstract

(57) [Summary] [Object] To provide a heat resistant vinyl chloride resin composition having high heat resistance and good moldability. A heat-resistant vinyl chloride resin composition comprising 100 parts by weight of a chlorinated vinyl chloride resin and 0.5 to 6 parts by weight of a mixture of a hydrotalcite compound and an alkyltin compound, wherein the chlorine is The chlorine content of the modified vinyl chloride resin is 59 to 71% by weight, and the hydrotalcite compound is subjected to decrystallization water treatment so that the amount of water of crystallization is 0 to 10% by weight. And the weight ratio of the alkyl tin compound is 1
5:85 to 95: 5, and the heat resistant vinyl chloride resin composition, wherein the alkyl tin compound is composed of an alkyl tin mercapto compound and an alkyl tin malate compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a heat resistant vinyl chloride resin composition.

[0002]

2. Description of the Related Art Vinyl chloride moldings have been used for construction materials, water pipes, agricultural pipes, joints, flat plates, etc. by taking advantage of their excellent properties such as mechanical strength, chemical resistance and oil resistance. It was However, it is difficult to use at high temperature because it has low heat resistance and is easily deformed by heating.

As a method for improving the heat resistance of a vinyl chloride type molded article, a method of post-chlorinating a vinyl chloride type resin is generally used. Chlorinated vinyl chloride moldings obtained by post-chlorination are used in fields that cannot be used with conventional vinyl chloride moldings, such as fire extinguishing sprinkler piping materials and industrial plates. However, conventional chlorinated vinyl chloride moldings, for example, when used for hot water supply pipes, are easily cracked or broken due to hot water deterioration due to long-term use or expansion deterioration due to water absorption, and their heat resistance is sufficient. Not really.

As a method of increasing the heat resistance of a chlorinated vinyl chloride type molded product, there is a method of adding a large amount of a heat stabilizer or a lubricant, but there is a problem that the kneading property is hindered and defective gelation occurs. Has been done.

Japanese Unexamined Patent Publication No. 55-80445 discloses a technique for solving this problem by adding a hydrotalcite compound as a heat stabilizer. However, those that require high heat resistance such as chlorinated vinyl chloride-based moldings cannot obtain sufficient thermal stability even if a hydrotalcite compound is added because the molding temperature is high, and There were also problems such as foaming during molding.

Japanese Patent Publication No. 3-28461 discloses a halogen-containing resin composition in which a hydrotalcite compound is added as a heat stabilizer to prevent initial coloring and foaming. However, although improvement in initial colorability and prevention of foaming have been achieved, satisfactory results have not been obtained for improvement in hot water deterioration of molded articles.

Further, when a tin-based stabilizer is used as the heat stabilizer, the heat resistance is remarkably lowered, and there is a problem in terms of moldability. When a large amount of a lubricant is added to improve moldability, heat resistance is further lowered and expansion deterioration due to water absorption occurs. At present, a chlorinated vinyl chloride resin composition having high heat resistance and good moldability has not been obtained.

[0008]

SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to provide a heat resistant vinyl chloride resin composition having high heat resistance and good moldability.

[0009]

The gist of the present invention is to provide a heat-resistant vinyl chloride resin composition with a chlorinated vinyl chloride resin 1
A heat-resistant vinyl chloride resin composition comprising 00 parts by weight and 0.5 to 6 parts by weight of a mixture of a hydrotalcite compound and an alkyltin compound, wherein the chlorine content of the chlorinated vinyl chloride resin is Is 59 to 71% by weight, the hydrotalcite compound is subjected to decrystallization water treatment, and the amount of water of crystallization is 0 to 10% by weight, and the weight ratio of the hydrotalcite compound to the alkyltin compound is Is 15:85 to 95: 5, and the alkyl tin compound is a compound represented by the following general formula (Ia) or a polymer having a repeating unit represented by the following general formula (Ib), alkyl tin mercapto. A compound represented by the following general formula (IIa), a compound represented by the following general formula (Ia)
A polymer having a repeating unit represented by Ib) or an alkyl tin maleate compound which is a compound represented by the following general formula (IIc), wherein the alkyl tin mercapto compound and the alkyl tin maleate compound are The weight ratio of is 10:10 to 1: 9.

[0010]

Embedded image

In the formula, R ¹ , R ² , R ³ and R ⁴ are independently an alkyl group having 1 to 10 carbon atoms, —SR ^a , or —
Represents S (CH ₂ ) _m COOR ^a . ^Ra is carbon number 2
24 represents an alkyl group. m represents an integer of 1 or more.
R ⁵ and R ⁶ independently represent an alkyl group having 1 to 10 carbon atoms. n represents an integer of 1 or more. R ⁷ , R ⁸ ,
R ⁹ and R ¹⁰ independently represent an alkyl group having 1 to 10 carbon atoms or —OCOCH═CHCOOR ^b . R ^b
Represents an alkyl group having 2 to 24 carbon atoms. R ¹¹ , R
¹² independently represents an alkyl group having 1 to 10 carbon atoms.
R ¹³ represents an alkyl group having 1 to 10 carbon atoms. R ¹⁴ , R
¹⁵ independently represents an alkyl group having 2 to 24 carbon atoms.

The chlorinated vinyl chloride resin used in the present invention (hereinafter referred to as "CPVC") has a chlorination degree of 59-.
It is 71% by weight. If it is less than 59% by weight, the heat resistance is not sufficient, and if it exceeds 71% by weight, the moldability is deteriorated, so the content is limited to the above range. The degree of chlorination within the above range can be selected according to the desired heat resistance. The method for adjusting the chlorination degree of CPVC is not particularly limited, and for example,
Examples thereof include a method of adjusting in the chlorination reaction stage, a method of blending a chlorinated vinyl chloride resin having a high degree of chlorination with a low chlorinated vinyl chloride resin or a normal vinyl chloride resin.

The method of chlorinating the CPVC is not particularly limited, and examples thereof include a known water suspension chlorination method and solution chlorination method of vinyl chloride resin. Industrially, the water suspension chlorination method is preferred. The vinyl chloride resin used in the production of the CPVC is not particularly limited, and examples thereof include those obtained by previously modifying a polymerizable monomer by copolymerization, graft polymerization, or the like. The polymerizable monomer is not particularly limited as long as it contains a radical reactive double bond and is copolymerizable with a vinyl chloride monomer by a radical polymerization initiator, and examples thereof include ethylene, propylene and butylene. Α-olefins; vinyl acetate,
Vinyl esters such as vinyl propionate; vinyl ethers such as butyl vinyl ether and cetyl vinyl ether; (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl acrylate, phenyl methacrylate; styrene, α-
Aromatic vinyls such as methylstyrene; vinylidene chloride,
Vinyl halides such as vinylidene fluoride; N- such as N-phenylmaleimide and N-cyclohexylmaleimide
Substituted maleimides and the like can be mentioned. These may be used alone or in combination of two or more.

The degree of polymerization of CPVC is preferably 800 to 1400 as the average degree of polymerization before chlorination. When it is 800 or less, the physical properties of the molded product are deteriorated, and when it exceeds 1400, molding becomes difficult. More preferably, 900 to 11
00.

The hydrotalcite compound used in the present invention has been subjected to decrystallization water treatment and has an amount of crystal water of 0 to 10% by weight. The hydrotalcite compound is obtained by pulverizing a natural ore such as manacenite, which is a double salt of magnesium and aluminum, or by subjecting a synthetic ore to a decrystallization water treatment.

The method of treating the above-mentioned hydrotalcite compound for decrystallization water is not particularly limited, and examples thereof include heat treatment. The processing temperature of the heat treatment is 1
80-350 degreeC is preferable, More preferably, it is 200-
280 ° C. The heat treatment time is preferably about 18 hours, more preferably 2 to 5 hours. When the treatment time is less than 180 ° C. or the treatment time is less than 18 hours, foaming occurs during molding, and the appearance of the molded product deteriorates.

The above-mentioned hydrotalcite compound is a higher fatty acid such as sodium stearate or sodium oleate; a wax; a titanium-based or silane-based coupling agent, etc. in order to improve compatibility with the chlorinated vinyl chloride resin. May be surface treated.

The alkyl tin compound used in the present invention comprises an alkyl tin mercapto compound and an alkyl tin maleate compound. The alkyl tin mercapto compound is a compound represented by the general formula (Ia) or a polymer having a repeating unit represented by the general formula (Ib).

In the formula, R ¹ , R ² , R ³ and R ⁴ are independently an alkyl group having 1 to 10 carbon atoms, —SR ^a , or —
Represents S (CH ₂ ) _m COOR ^a . As the alkyl group, a methyl group, a butyl group, an octyl group and the like are preferable.
R ^a represents an alkyl group having 2 to 24 carbon atoms. Preferably, it is an alkyl group having 11 to 17 carbon atoms. R ⁵ , R ⁶
Each independently represents an alkyl group having 1 to 10 carbon atoms. Of these, a methyl group, a butyl group, an octyl group and the like are preferable.

Examples of the alkyl tin mercapto compound include dialkyl tin dialkyl mercaptides represented by the following general formula (III) and general formula (IV) below.
Examples thereof include dialkyltin bis (mercaptocarboxylic acid alkyl ester) salts represented by and dialkyltin mercaptocarboxylic acid salt polymers represented by the following general formula (V).

[0021]

Embedded image

In the formula, R represents an alkyl group having 1 to 10 carbon atoms. R ¹⁶ represents an alkyl group having 2 to 24 carbon atoms.
R ¹⁷ represents an alkyl group having 2 to 24 carbon atoms. m is 1
Represents the above integers. p represents an integer of 1 or more.

The alkyl tin maleate compound is a compound represented by the general formula (IIa) or the general formula (I).
It is a polymer having a repeating unit represented by Ib).

In the formula, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are independently an alkyl group having 1 to 10 carbon atoms, or --OCOCH.
Represents CHCOOR ^b . As the alkyl group, a methyl group, a butyl group, an octyl group and the like are preferable. R ^b is
It represents an alkyl group having 2 to 24 carbon atoms. Preferably, it is an alkyl group having 11 to 17 carbon atoms. R ¹¹ and R ¹² independently represent an alkyl group having 1 to 10 carbon atoms. Of these, a methyl group, a butyl group, an octyl group and the like are preferable.

Examples of the alkyl tin maleate compound include dialkyl tin bis (maleic acid alkyl ester) salts represented by the following general formula (VI) and bis (dialkyl tin maleic acid represented by the following general formula (VII). Alkyl ester) maleate, the following general formula (VI
Examples thereof include dialkyl tin maleate polymers represented by II).

[0026]

[Chemical 4]

In the formula, R ¹⁸ represents an alkyl group having 2 to 24 carbon atoms. R ¹⁹ represents an alkyl group having 2 to 24 carbon atoms. q represents an integer of 1 or more.

The heat-resistant vinyl chloride resin composition of the present invention comprises 100 parts by weight of the chlorinated vinyl chloride resin, 0.5 to 6 parts by weight of the hydrotalcite compound and the alkyltin compound. When the addition amount of the hydrotalcite compound and the alkyl tin compound is less than 0.5 part by weight, the thermal stability is lowered, and when the amount is more than 6 parts by weight, the thermal stabilizing effect is saturated and the softening temperature is Since it decreases, it is limited to the above range.

In the present invention, the weight ratio of the hydrotalcite compound to the alkyl tin compound is 15:85.
~ 95: 5. If the ratio of the hydrotalcite compound to the alkyltin compound 5 exceeds 95, the thermal stability becomes poor and the range of molding temperature becomes narrow,
When the ratio of the alkyl tin compound to the hydrotalcite compound 15 exceeds 85, the heat resistance is lowered, so the content is limited to the above range.

The alkyltin compound comprises the alkyltin mercapto compound and the alkyltin maleate compound, and the weight ratio of the alkyltin mercapto compound to the alkyltin maleate compound is 10: 0-1. : 9. When the ratio of the alkyl tin maleate compound to the alkyl tin mercapto compound 1 exceeds 9, the thermal stability is improved, but uneven flow occurs at the time of molding and the appearance of the molded product is deteriorated, so the content is limited to the above range. It

In the present invention, if necessary, for example, di-2-ethylhexyl phthalate, di-adipate di-
Plasticizers such as 2-ethylhexyl; lubricants such as polyethylene wax, ester wax, stearic acid wax, montanic acid wax, calcium carbonate; pigments;
Fillers such as glass fibers; impact modifiers such as acrylic rubber and MBS; antistatic agents; flame retardants; processing aids; UV absorbers and the like may be added.

The heat-resistant vinyl chloride resin composition of the present invention contains the above-mentioned chlorinated vinyl chloride resin, the above-mentioned hydrotalcite compound, the above-mentioned alkyl tin compound, the above-mentioned additives and the like, for example, a conventional mixing device such as a Henschel mixer It is obtained by mixing with.

The heat-resistant vinyl chloride resin composition can be molded by usual methods such as extrusion pipe molding, extrusion sheet molding, injection molding, hot press molding, etc. It can be molded into plates, films, etc.

[0034]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

1. Decrystallization water treatment of hydrotalcite compound The hydrotalcite compound (11% by weight of water of crystallization) was heated at 220 ° C for 5 hours to carry out dehydration treatment to adjust the amount of water of crystallization to 2.5% by weight. The hydrotalcite compound (11% by weight of water of crystallization) was heated at 240 ° C. for 5 hours to perform dehydration treatment, and the amount of water of crystallization was set to 0% by weight. Measurement of water of crystallization About 10 mg of hydrotalcite compound was analyzed by a thermogravimetric analyzer (TG / DTA200 manufactured by Seiko Instruments Inc.).
Weight loss was measured when the temperature was raised from room temperature to 220 ° C. at a rate of temperature rise of 5 ° / min, and the amount of reduction with respect to the total amount was expressed as% by weight to give the water of crystallization. 2. Examples 1 to 11 and Comparative Examples 1 to 6 Predetermined amount of chlorinated vinyl chloride resin (manufactured by Tokuyama Sekisui Industry Co., Ltd.) shown in Tables 1 and 2, hydrotalcite compound, alkyltin compound (alkyltin mercapto compound, alkyl) Tin malate compound), MBS-based strengthening agent (BTA-751 manufactured by Kureha Chemical Industry Co., Ltd.), ester-based lubricant (SL
02), stearic acid and a polyethylene-based lubricant (HIWAX220, manufactured by Mitsui Petrochemical Industry Co., Ltd.) were heated to 130 ° C. with a Henschel mixer and mixed, and then a pipe (diameter 20 mm, diameter: 20 mm, biaxial, biaxial). ) Extrusion evaluation was performed and the appearance of the pipe was visually evaluated. Appearance has no problem ○, slightly streaky, wavy △
Those that were clearly not good in appearance were marked with x.

In Tables 1 and 2, as dioctyltin malate, "ONR79F (trade name)" manufactured by Sansha Kisei Co., Ltd.
The dioctyl tin mercapto 1 is "ONZ142F (trade name)" manufactured by Sansha Machine Synthesis, and the dioctyl tin mercapto 2 is "SNT461" manufactured by Sansha Machine Synthesis.
K (trade name) ", as dibutyltin malate," BM (N) (trade name) "manufactured by Sankyo Machine Synthesis Co., Ltd., and dibutyltin mercapto," JF10B manufactured by Sankyo Machine Synthesis Co., Ltd. "
(Product name) "was used.

In Tables 1 and 2, the values in parentheses for the hydrotalcite compounds A, B and C represent the water content of crystallization.

The pipes obtained in the above Examples and Comparative Examples were evaluated as follows, and the results are shown in Tables 1 and 2. Roll heat stability 8-inch roll (made by Yasuda Seiki Co., TEST MI
(XING ROLL 191-TM) was used to measure the time from the winding of the roll at 200 ° C. to the blackening. Water absorption The pipe sample cut to a length of 2 cm was immersed in hot water of 130 ° C. (pressure: 1.8 kgf / cm ² ) for 3 days, and the weight change rate was measured. Softening temperature The Vicat softening temperature was measured according to JIS K7206. External appearance of the pipe The appearance of the extruded pipe was visually evaluated, and a good appearance was rated as ⊚ and a poor appearance was rated as x.

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

EFFECTS OF THE INVENTION The heat-resistant vinyl chloride resin composition of the present invention has the above-mentioned constitution, so that it has high heat resistance and good moldability, and the obtained molded article has high heat resistance.
With excellent hot water resistance and good appearance, heat resistant hot water supply pipe,
It is preferably used in places where heat resistance is required, such as plant pipes.

Claims (1)

[Claims] 1. A 100 parts by weight of a chlorinated vinyl chloride resin,
And a heat-resistant vinyl chloride resin composition comprising 0.5 to 6 parts by weight of a mixture of a hydrotalcite compound and an alkyltin compound, wherein the chlorine content of the chlorinated vinyl chloride resin is 59 to 71% by weight, the hydrotalcite compound is subjected to decrystallization water treatment, and the amount of water of crystallization is 0 to 10% by weight, and the weight ratio of the hydrotalcite compound to the alkyltin compound is
15:85 to 95: 5, wherein the alkyl tin compound is an alkyl tin mercapto compound which is a compound represented by the following general formula (Ia) or a polymer having a repeating unit represented by the following general formula (Ib). , The following general formula (I
Ia), a polymer having a repeating unit represented by the following general formula (IIb), or an alkyl tin maleate compound which is a compound represented by the following general formula (IIc), The heat-resistant vinyl chloride resin composition, wherein the weight ratio of the alkyltin mercapto compound to the alkyltin maleate compound is from 10: 0 to 1: 9. Embedded image In the formula, R ¹ , R ² , R ³ and R ⁴ independently have 1 carbon atom.
10 alkyl group, -SR ^a, or, -S (CH ₂₎
represents _m COOR ^a . R ^a represents an alkyl group having 2 to 24 carbon atoms. m represents an integer of 1 or more. R ⁵ , R
⁶ independently represents an alkyl group having 1 to 10 carbon atoms.
n represents an integer of 1 or more. R ⁷ , R ⁸ , R ⁹ , R
¹⁰ is independently an alkyl group having 1 to 10 carbon atoms, or
Represents -OCOCH = CHCOOR ^b . R ^b represents an alkyl group having 2 to 24 carbon atoms. R ¹¹ and R ¹² independently represent an alkyl group having 1 to 10 carbon atoms. R ¹³ represents an alkyl group having 1 to 10 carbon atoms. R ¹⁴ and R ¹⁵ independently represent an alkyl group having 2 to 24 carbon atoms.