JPH07292006A - Vinyl chloride copolymer and its production - Google Patents

Abstract

PURPOSE:To produce a vinyl chloride copolymer which can give a matted article having a smooth silky surface with an excellent matte effect and making an impression of a quality article. CONSTITUTION:This production process is the one for producing a vinyl chloride copolymer by suspension-polymerizing a polymerizable monovinyl compound mixture (VCM) based on a vinyl chloride monomer, polyalkylene glycol dimethacrylate and/or polyalkylene glycol diacrylate in the presence of an oil-soluble polymerization initiator in an aqueous medium, wherein a nonionic surfactant with an HLB in the range: 1<=HLB<=10 and 0.01wt.% or below, based on VCM, polymerization inhibitor are used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a vinyl chloride copolymer and a vinyl chloride copolymer which can provide a high-quality matte molded article having excellent matte performance and a smooth silky surface. A manufacturing method for obtaining the same.

[0002]

2. Description of the Related Art A vinyl chloride molded product having a matte surface (hereinafter, abbreviated as a matte product) is preferred because it has a high-grade appearance compared to a glossy molded product. The matte product can be easily obtained by injection molding, extrusion, calendering or the like. However, when a vinyl chloride homopolymer is used, the matte product must be molded at a low temperature. Kneading cannot be performed sufficiently and mechanical properties represented by tensile strength are poor. When molding at high temperature to improve the physical properties,
Luster is generated on the surface, deteriorating the sense of quality.

Other methods for obtaining a matte product include a method of forming a grain on the surface of a molded product and a method of applying a matting paint to the molded product, but the former is difficult to apply to extrusion molding. However, the latter has a problem that the number of molding steps and working time increase, resulting in an increase in cost. There is also a method in which a large amount of filler such as heavy calcium carbonate is added to the resin to obtain a matte product, but the product is susceptible to aging and deterioration due to heating, and tensile strength, brittleness, brittle temperature, oil resistance ,
Physical properties such as impact resilience are extremely deteriorated.

There is also a method of copolymerizing VCM and a crosslinking monomer such as allyl methacrylate, diallyl phthalate or diallyl adipate in order to impart a matting property to the resin itself. The type of crosslinking monomer to be copolymerized or It is preferably used because the matting performance can be easily adjusted depending on the amount used. However, the matte product obtained by this method is
It is difficult to micro-roughen the unevenness of the surface of the molded product, that is, to make the surface matte like a silk.
If you try to make the surface smooth silky, the matte performance will deteriorate and gloss will occur, and if you try to improve the matteness, the surface roughness will increase and you will lose the sense of quality. is there. As described above, in the conventional technique, it is not possible to simultaneously remove the surface gloss and make the surface silky, and a matte product having these performances is currently available. It was the actual situation.

[0005]

DISCLOSURE OF THE INVENTION The object of the present invention is to solve the above-mentioned drawbacks of the prior art and to obtain a high-grade matte product having excellent matte performance and smooth silky surface. It is intended to provide a vinyl chloride copolymer, and to provide a method for producing the vinyl chloride copolymer.

[0006]

Means for Solving the Problems As a result of intensive investigations by the inventors of the present invention, a vinyl chloride copolymer has been obtained which gives a high-grade matte product having excellent matte performance and smooth silky surface. , Such vinyl chloride copolymer is
When a vinyl chloride copolymer is produced by suspension-polymerizing AGE with an AGE in an aqueous medium using an oil-soluble polymerization initiator,
The inventors have found that it can be obtained by using a nonionic surfactant having a B value and a polymerization inhibitor, and have completed the present invention.

The present invention has the following configuration. (1) When VCM or the like containing VCM as a main component and PAGE are suspension-polymerized in an aqueous medium using an oil-soluble polymerization initiator to produce a vinyl chloride copolymer, 1 ≦ HLB ≦ 10 nonionic 0.01% by weight based on VCM and other surfactants
A method for producing a vinyl chloride copolymer using a polymerization inhibitor in the following range. (2) The method for producing a vinyl chloride copolymer according to the item (1), wherein the polymerization inhibitor is methylethylhydroquinone or hydroquinone. (3) A vinyl chloride copolymer obtained by the production method according to item (1) or (2).

The VCM used in the present invention means VCM
And a polymerizable compound having a vinyl group at one end that can be copolymerized with VCM, and the polymerizable compound is VCM.
It is not particularly limited as long as it can be copolymerized with, but specifically, an alkyl vinyl ester such as vinyl acetate,
Examples thereof include alkyl vinyl ethers such as cetyl vinyl ether, α-monoolefin monomers such as ethylene or propylene, acrylic acid alkyl esters such as methyl acrylate, and methacrylic acid alkyl esters such as methyl methacrylate. it can.

The PAGE used in the present invention is polyalkylene glycol dimethacrylate and / or polyalkylene glycol diacrylate, which is represented by the following chemical formulas 1 and 2, and n is 1 to 10. Is preferred. When it exceeds 10, the matte fisheyes obtained are increased. Further, x is 2 to 60, preferably 4 to 50, and more preferably 6 to 30. When x is small, PAGE becomes volatile, and an irritating odor is generated, which deteriorates the working environment. On the other hand, when x is too large, the copolymerization reaction becomes difficult, and unreacted PAGE causes blooming of the matte product.

[0010]

[Chemical 1]

[0011]

[Chemical 2]

Specific examples of polyalkylene glycol dimethacrylate include polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
Examples include 1,4-butylene glycol dimethacrylate and neopentyl glycol dimethacrylate. Specific examples of the polyalkylene glycol diacrylate include polyethylene glycol diacrylate, polypropylene glycol diacrylate, and 1,3.
-Butylene glycol diacrylate, 1,4-butylene glycol diacrylate, neopentyl glycol diacrylate and the like can be exemplified.

The charge amount of PAGE used in the present invention is VC
0.05 to 5.0% by weight, preferably 0.
1 to 2.0% by weight is preferable. If it is less than 0.05% by weight, the effect of the present invention is difficult to obtain, and conversely, if it is more than 5.0% by weight, the surface of the matte product may be roughened.

As the oil-soluble polymerization initiator used in the present invention, lauroyl peroxide, benzoyl peroxide, tertiary butyl peroxyneodecanoate, acetylcyclohexyl sulfonyl peroxide, tertiary butyl peroxypivalate, α-cumin Ruperoxypivalate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3,5,5
-Trimethylhexanoyl peroxide, bis (4-
Tert-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-3-methoxy-3-methylbutylperoxydicarbonate, di-secondary butylperoxydicarbonate, α-cumylperoxyneo Examples thereof include organic peroxides such as decanoate and azo compounds such as α, α′-azobis-4-methoxy-2,4-dimethylvaleronitrile, which are used as one kind or a mixture of two or more kinds. Good to do.

The nonionic surfactant used in the present invention must have an HLB value usually used as an index of hydrophilic-lipophilic balance in the range of 1≤HLB≤10. HLB is less than 1 or 10
If a larger nonionic surfactant is used, a vinyl chloride copolymer having the excellent effect of the present invention cannot be obtained.

Specific examples of the nonionic surfactant include sorbitan laurate, sorbitan fatty acid esters such as sorbitan oleate, diglycerin stearate, and the like.
Examples thereof include polyglycerin fatty acid ester such as diglycerin oleate and polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether. Further, the charged amount of the nonionic surfactant is 0.01 to 0.2% by weight, preferably 0.05 to 0.2% by weight based on VCM and the like.
0.15 wt% is good.

The polymerization inhibitor used in the present invention is preferably methylethylhydroquinone or hydroquinone. The amount of the polymerization inhibitor used is VCM and the like.
It must be 0.01% by weight or less. If it is more than 0.01% by weight, the progress of the polymerization reaction is hindered. It is preferably 0.0005 to 0.01% by weight, and particularly preferably
0.001 to 0.005% by weight is desirable.

Further, within a range that does not impair the effects of the present invention,
Other additives that are usually used in suspension polymerization include stabilizers that can prevent scale adhesion to the inner wall of the polymerization vessel, antioxidants, chain transfer agents that adjust the average degree of polymerization, and unreacted VCM recovery. Defoaming agent to prevent foaming at the time of use or when using a reflux condenser, PH for adjusting the pH of the polymerization water medium
There is no problem even if a regulator and a foaming agent are added.

In the suspension polymerization according to the present invention, PAG
E may be charged all at once at the beginning of polymerization or may be charged in several times during the reaction. The oil-soluble polymerization initiator may be added to water charged at the beginning of the polymerization, or may be added to the polymerization system together with each additive. Further, the polymerization initiator,
It may be added in two or more portions. The nonionic surfactant and the polymerization inhibitor may be separately charged all at once at the beginning of the polymerization, but it is effective to premix them in PAGE and to charge them together with the PAGE into the polymerization system.

The suspension polymerization may be arbitrarily set within a polymerization temperature range of 35 ° C to 75 ° C, preferably 52 ° C to 69 ° C.
C., more preferably 57 to 65.degree.
The suspension polymerization may be carried out by changing the polymerization temperature in two or more steps. In particular, the processability is significantly improved, the rotation of the bank can be made extremely smooth in the calendar process, and the extrusion amount can be increased in the extrusion process. 2 ℃ from the polymerization temperature
It is effective to set different temperatures of 20 to 20 ° C. The polymerization temperature in the later stage can be lower or higher than the polymerization temperature in the previous stage, but if the difference in the polymerization temperature is small, the temperature in the latter stage can be lowered or the temperature can be increased. However, when the difference in the polymerization temperature is large, it is better to raise the temperature of the subsequent stage to a higher temperature in order to maintain the activity of the polymerization initiator and to easily apply it to the existing jacketed polymerization vessel. Is practical.

[0021]

The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto. The evaluation methods carried out in Examples and Comparative Examples were based on the following methods.

(1) Matting property Using the polymers obtained in Examples 1-5 and Comparative Examples 1-8, the following compositions A and B were obtained. next,
Of the obtained composition, compound A was kneaded with a mixing roll set at 160 ° C. and compound B was mixed with a mixing roll set at 170 ° C. for 10 minutes each.
A film having a thickness of 0.32 mm was obtained from the film having a thickness of 0.3 mm and the composition B, and the matte state of the obtained film surface was visually observed and judged according to the following criteria. Judgment ○: The gloss is very well lost. Δ: A little glossy. X: No gloss and remarkable gloss <Compound A> Vinyl chloride copolymer or vinyl chloride homopolymer 100 g, DOP 50 g, epoxy stabilizer 2
g, Ca-St 0.6 g, Zn-St 0.9 g mixture. <Compound B> Vinyl chloride copolymer or vinyl chloride homopolymer 100 g, dibutyltin malate 3 g, ultramarine blue 0.
01 g of mixture. (2) Surface property The surface property of the film obtained in the above-mentioned test item matte property was visually observed and judged according to the following criteria. Judgment ⊚: Has a supple surface property (silk state) that gives a feeling like a tanned leather surface. ◯: The unevenness is not visually observed, but the surface is slightly rough and does not feel like a tanned leather surface. Δ: The surface is a little rough and the unevenness is rough. X: The surface is extremely rough.

(Examples 1 to 3, Comparative Examples 1 to 3) Internal volume 2
84 liters of pure water was charged in a polymerization vessel made of stainless steel of 00 liters, and a saponification degree of 7 was added thereinto as a dispersion stabilizer.
The viscosity of a 0.5% by mole, 4% aqueous solution at 20 ° C. is 6.
4 cps, 13.7 g of polyvinyl alcohol having a carbonyl group content of 0.53 mol% and methyl cellulose 10.8
g, and as an oil-soluble polymerization initiator, 4.1 g of a 70% toluene solution of tertiary butyl peroxyneodecanoate, 70% of cumylperoxyneodecanoate
18.4 g of a toluene solution was added. Furthermore, 211 g of PAGE shown in Table 1 (1.0% by weight with respect to VCM),
21.1 g of sorbitan laurate (HLB = 7.4)
(0.1% by weight relative to VCM), hydroquinone 0.
63 g (0.003% by weight with respect to VCM) and V
Charge CM21.1Kg and stir the polymerization tank for 5 times.
After the temperature was raised to 8 ° C. and the polymerization reaction was carried out for 6 hours, the unreacted VCM existing in the contents was recovered outside the system, and the reaction product in the polymerization tank was washed with water, dehydrated and dried to obtain a vinyl chloride copolymer. And a vinyl chloride homopolymer was obtained. The obtained polymer was used for the above-mentioned evaluation test, and the results are shown in Table 1.

(Example 4, Comparative Examples 4 to 5) Internal volume 200
A liter stainless steel polymerization tank was charged with 138 liters of pure water, and a saponification degree of 7 was used as a dispersion stabilizer.
The viscosity of a 0.5% by mole, 4% aqueous solution at 20 ° C. is 6.
4 cps, carbonyl group content 0.53 mol% polyvinyl alcohol 50.6 g and methyl cellulose 50.6
g was added, and as an oil-soluble polymerization initiator, 27.1 g of a 70% toluene solution of tertiary butyl peroxy neodecanoate and 70% of cumyl peroxy neodecanoate were added.
% Toluene solution 19.4 g, polyethylene glycol diacrylate as PAGE (Chemical formula 2: n = 2, x = 1
4) 828.5 g (1.8% by weight based on VCM) was added. Furthermore, 45.2 g of various nonionic surfactants shown in Table 2 (0.1% by weight with respect to VCM), 1.36 g of hydroquinone (0.003% by weight with respect to VCM), and 40.5 g of VCM. After charging 2 Kg and heating the polymerization tank to 58 ° C. with stirring and performing a polymerization reaction for 6 hours, unreacted VCM existing in the contents was recovered outside the system, and the reaction product in the polymerization tank was washed with water. It was dehydrated and dried to obtain a vinyl chloride homopolymer. The obtained polymer was used for the above-mentioned evaluation test, and the results are shown in Table 2.

(Examples 5-6, Comparative Examples 6-7) Internal volume 2
138 liters of pure water was charged in a polymerization tank made of stainless steel of 00 liters, and as a dispersion stabilizer, the saponification degree was 70.5 mol%, the viscosity of a 4% aqueous solution at 20 ° C. was 6.4 cps, and the carbonyl group content was 0.53 mol% polyvinyl alcohol 50.6 g and methyl cellulose 5
0.6 g was added, and as an oil-soluble polymerization initiator, 25.8 g of a 70% toluene solution of tertiary butyl peroxy neodecanoate, 19.4 g of a 70% toluene solution of cumyl peroxy neodecanoate, and as PAGE Polyethylene glycol diacrylate (Chemical formula 2: n = 1, x
= 9) 828.5 g (1.8 wt% with respect to VCM) was added. Further, diglycerin stearate (HLB = 5.7) as a nonionic surfactant and methylethylhydroquinone as a polymerization inhibitor were added in an amount shown in Table 3, 45.2 Kg of VCM was charged, and the polymerization was performed while stirring. After the temperature of the tank was raised to 58 ° C and the polymerization reaction was carried out for 6 hours, the unreacted VCM existing in the contents was recovered outside the system, and the reaction product in the polymerization tank was washed with water, dehydrated and dried, and vinyl chloride alone was used. A polymer was obtained. Using the obtained polymer in the evaluation test described above,
The results are shown in Table 3.

[0026]

As shown in Table 1, when a crosslinkable comonomer other than PAGE is used, a matte product having a matte and silky surface property as in the present invention cannot be obtained.
When the HLB value of the nonionic surfactant used is less than 1 or the HLB value is more than 10, it is clear that the matte product obtained cannot be provided with the silky surface property as in the present invention. Is. Further, it can be seen from Table 3 that when a nonionic surfactant and a specific amount of a polymerization inhibitor are added, a matte product having extremely excellent matteness and surface property can be obtained. As described above, the vinyl chloride copolymer obtained by using the production method of the present invention eliminates the gloss of the surface of the molded product, which cannot be obtained by the conventional technique, and makes the surface of the molded product silky. It is a useful material for automobiles, machines, electricity, medical care, construction, etc. is there.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

Claims (3)

[Claims] 1. A monovinyl-polymerizable compound mixture (hereinafter, abbreviated as VCM) having a vinyl group containing vinyl chloride monomer (hereinafter, abbreviated as VCM) as a main component, and polyalkylene glycol dimethacrylate and / or poly. When a vinyl chloride copolymer is produced by suspension-polymerizing alkylene glycol diacrylate (hereinafter, abbreviated as PAGE collectively) with an oil-soluble polymerization initiator in an aqueous medium, 1 ≦ HLB ≦ 10 is satisfied. Nonionic surfactant and VC
A method for producing a vinyl chloride copolymer, which comprises using 0.01% by weight or less of a polymerization inhibitor with respect to M and the like. 2. The method for producing a vinyl chloride copolymer according to claim 1, wherein the polymerization inhibitor is methylethylhydroquinone or hydroquinone. 3. A vinyl chloride copolymer obtained by the production method according to claim 1.