JP2515013B2 - Vinyl chloride resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition. More specifically, the present invention relates to a vinyl chloride resin composition which exhibits excellent impact resistance over conventional products while maintaining excellent transparency of the vinyl chloride resin.

[Problems to be solved by the prior art / invention] As a reinforcing agent for improving impact resistance without impairing the transparency of vinyl chloride resin, butadiene rubber was graft-polymerized with methyl methacrylate, styrene, or the like. So-called
Since the development of the MBS resin, many methods have been developed for improving the impact strength without impairing the transparency of the vinyl chloride resin (for example, JP-A-59-221317).

However, there is still a strong demand for quality improvement in this field, and further improvement is awaited.

As a method of significantly improving the impact resistance imparting ability of a vinyl chloride resin reinforcing agent, a method of increasing the butadiene content in the reinforcing agent is well known. Therefore, attempts have been made to increase the proportion of the rubber component in the reinforcing agent or increase the butadiene content in the rubber component. But,
In the former method of increasing the ratio of the rubber component, since the ratio of the rubber component exceeds 65% (weight%, the same applies below), the graft copolymer agglomerates at the time of production and a good powder cannot be obtained. There is a big problem that the transparency of the final molded product after mixing with the vinyl chloride resin decreases.
Further, the latter method of increasing the butadiene content in the rubber component has a big problem that the transparency of the final molded product is significantly lowered.

[Means for Solving the Problem] The present invention is a method for increasing the impact resistance imparting ability of a reinforcing agent of vinyl chloride resin, a method of increasing the ratio of a rubber component in the reinforcing agent, and a butadiene content in the rubber component. It was made with the aim of solving the drawbacks of transparency and difficult powdering, which were the drawbacks of the method, together with the method of increasing the rate, and achieving both transparency and extremely high impact resistance. (A) Butadiene-based polymer consisting of 82-10% of butadiene and 18-0% of other vinyl monomer copolymerizable therewith
In the presence of 65 to 85 parts (parts by weight, the same applies hereinafter), 0.1 to 3 parts of the crosslinkable monomer and 0 to 3 parts of at least one of alkyl acrylate and alkyl methacrylate were added and reacted. After that, aromatic vinyl monomer 50-95
%, Vinyl cyanide monomer 0.1-40% and other vinyl monomer 0-40% copolymerizable therewith 35
Impact resistance consisting of 3 to 30 parts of a resin obtained by emulsion polymerization of 15 to 15 parts with a butadiene-based polymer to a total amount of 100 parts and (B) a vinyl chloride resin of 97 to 70 parts, and The present invention relates to a vinyl chloride resin composition having excellent transparency.

In the present invention, (1) in order to increase the butadiene content of the reinforcing agent, the ratio of the rubber component is significantly increased, and the butadiene content in the rubber component is increased (2) In order to solve the problem of difficult powdering To react the rubber terax with a crosslinkable monomer, etc. (3) In order to prevent a decrease in the refractive index of the reinforcing agent due to an increase in the butadiene content in the reinforcing agent, a graft component-containing aromatic vinyl monomer is used. (4) Achieving the above-mentioned object by introducing a vinyl cyanide monomer in order to prevent deterioration of physical properties due to an increase in the proportion of the aromatic vinyl monomer in the graft component. This is a significant difference from the previously disclosed method of simply using acrylonitrile as one component of the graft portion.

[Examples] The butadiene-based polymer used in the present invention can be obtained by, for example, emulsion-polymerizing a monomer consisting of butadiene and a vinyl monomer copolymerizable therewith.

The copolymerizable vinyl monomer is used when it is necessary to increase the refractive index of the butadiene-based polymer or impart a crosslinked structure, and depending on the properties to be improved and the degree thereof, it is used. The type and amount of the vinyl monomer to be used vary, but for example, the amount of vinyl monomer used is usually 0.1 to 8% or more in the butadiene-based polymer. Is preferable from the standpoint of effectively improving.

Specific examples of the vinyl monomer copolymerizable with butadiene include aromatic vinyl monomers such as styrene, vinyl cyanide monomers such as acrylonitrile, and carbon number 1 to 1 such as ethyl acrylate or butyl acrylate. Examples thereof include acrylic acid alkyl esters having an alkyl group of about 5 and crosslinkable monomers such as divinylbenzene, but are not limited thereto. These may be used alone or in combination of two or more.

When the butadiene-based polymer is produced, the butadiene and other vinyl monomer copolymerizable therewith are used in a proportion of butadiene 82 to 100%, preferably 85 to 99.5% with butadiene. Other possible vinyl monomers 18 ~
It is 0%, preferably 15 to 0.5%. If the proportion of butadiene used is less than 82%, the impact strength of the obtained vinyl chloride resin composition will not reach the same level as in the conventional case, which is not preferable. Polymerization uses these monomers
The polymerization may be carried out in stages, for example, a usual emulsion polymerization, but about 62 to 80% of butadiene and about 18 to 0% of other vinyl monomer copolymerizable therewith are first polymerized, and then the remaining It is more preferable to polymerize the above butadiene from the viewpoint of transparency.

The butadiene-based polymer thus obtained has a butadiene content of 82 to 100%, which is higher than that of conventional reinforcing agents, and therefore the impact strength of the obtained vinyl chloride-based resin composition can be significantly improved.

In the present invention, the butadiene-based polymer 65 to 85
Part, preferably 70-80 parts, in the presence of 0.1 parts of the crosslinkable monomer.
.About.3 parts and 0 to 3 parts of at least one of acrylic acid alkyl ester and methacrylic acid alkyl ester are reacted.

The crosslinkable monomer serves to help the graft component polymerized next to the butadiene-based polymer to polymerize not on the inside of the butadiene-based polymer but on the surface, and the graft copolymer is agglomerated at the time of production to be a good powder. It is an ingredient to prevent the problem of being hard to get.

In addition, at least one kind of the acrylic acid alkyl ester and the methacrylic acid alkyl ester (hereinafter, also referred to as “(meth) acrylic acid alkyl ester”) has transparency of the graft copolymer obtained by reacting the crosslinkable monomer. It is a component used if necessary when finely adjusting the impact strength. Therefore, when the (meth) acrylic acid alkyl ester is used, it is usually preferable to use about 0.5 parts or more with respect to 65 to 85 parts of the butadiene-based polymer for the above purpose. When it exceeds 3 parts, the powder state of the reinforcing agent becomes better and better, but the impact resistance-imparting ability decreases. When the butadiene-based polymer exceeds 70 parts, 0.3 to 3 parts of the crosslinkable monomer is preferably used.

Specific examples of the crosslinkable monomer include, for example, divirbenzene, monoethylene glycol dimethacrylate,
Examples thereof include polyethylene glycol dimethacrylate, but are not limited thereto.

Further, the (meth) acrylic acid alkyl ester is preferably a (meth) acrylic acid alkyl ester having an alkyl group having about 1 to 5 carbon atoms, and such (meth) acrylic acid alkyl ester Specific examples thereof include, but are not limited to, butyl acrylate and methyl methacrylate. These may be used alone or in combination of two or more.

The conditions for reacting the crosslinkable monomer and the (meth) acrylic acid alkyl ester in the presence of the butadiene-based polymer are not particularly limited. For example, when the butadiene-based polymer is prepared by an emulsion polymerization method, After the polymerization reaction of the butadiene-based polymer, the crosslinkable monomer and the (meth) acrylic acid alkyl ester may be added to the reaction solution and the reaction may be performed under the same conditions as the polymerization.

Aromatic vinyl monomer 50 to 95%, preferably 70 to 90%, vinyl cyanide monomer 0.1 to 40%, preferably 10 to 30% and co-polymerized with these are added to the butadiene polymer after the above reaction. Polymerizable other vinyl monomer 0-40%, preferably 0 or 0.01-20% monomer 35-15 parts, preferably 30-20 parts butadiene and other vinyl copolymerizable therewith The total amount with the butadiene-based polymer consisting of monomers
Graft-polymerized to 100 parts.

In the graft component composed of the aromatic vinyl monomer, the vinyl cyanide monomer and the other vinyl monomer copolymerizable therewith, the aromatic vinyl monomer increases the butadiene content in the reinforcing agent. The vinyl cyanide monomer is a component used to prevent the decrease in the refractive index of the reinforcing agent that accompanies it and to bring the refractive index of the reinforcing agent to a value close to that of the vinyl chloride resin. Another vinyl monomer that is a component used to prevent deterioration of physical properties such as transparency, impact resistance, and powder properties due to an increase in the proportion of group vinyl monomers, and is copolymerizable with these. Is used when it is necessary to improve properties such as processability of the graft copolymer, and the type and amount of the vinyl monomer used depends on the properties and degree of improvement. Change. Therefore, if the proportion of aromatic vinyl monomer in the graft component is less than 50%, the refractive index of the reinforcing agent will be too small, and if it exceeds 95%, the physical properties such as transparency, impact resistance and powder properties will deteriorate. Grows larger. Further, when the ratio of the vinyl cyanide monomer is less than 0.1%, the effect of using it cannot be substantially obtained, and when it exceeds 40%, the physical properties such as transparency and impact resistance are deteriorated. Furthermore, if the proportion of vinyl monomers copolymerizable with these exceeds 40%, it becomes difficult to bring the refractive index of the graft copolymer close to that of the vinyl chloride resin.

Specific examples of the aromatic vinyl monomer are styrene and the like; specific examples of the vinyl cyanide monomer are acrylonitrile and the like; specific examples of other copolymerizable vinyl monomers are butyl acrylate and the like. Examples of the acrylic acid alkyl ester having an alkyl group of 1 to 5, methyl methacrylate and the like, methacrylic acid alkyl ester having an alkyl group of 1 to 5 carbon atoms, acrylic acid, methacrylic acid, and the like. It is not limited. Further, these monomers may be used alone or in combination of two or more kinds.

The graft polymerization method is not particularly limited, and a usual method,
For example, it may be carried out by a method such as emulsion polymerization, or it may be carried out by a method in which a butadiene-based polymer latex is coagulated / expanded with an acid and then polymerized.A latex is added during the graft polymerization by adding a water-soluble electrolyte. It may be performed by a method such as a method of causing it. Further, the method of adding monomers in the graft polymerization is not particularly limited, and may be a multi-step addition method in which the monomer composition of each step is the same or different, or a batch addition method.

In order to improve the transparency of the final molded product, the weight average particle size of the graft copolymer latex is 500 to 2500Å
It is preferable to make the refractive index of the reinforcing agent sufficiently close to the refractive index of the vinyl chloride resin. Specifically, the difference between the refractive index of the reinforcing agent and the refractive index of the vinyl chloride resin is preferably set to about 0 to 0.01.

The amount of the graft component in 100 parts of the graft copolymer minus the crosslinking monomer and (meth) acrylic acid alkyl ester is 15 to 35 parts as described above, but the amount is less than 15 parts. If so, the graft copolymer will be agglomerated during production, and good powder will not be obtained, and if it exceeds 35 parts, the degree of improvement in impact strength will be small.

The graft copolymer latex obtained as described above is added with an acid or a salt or both, coagulated, heat-treated, washed, dehydrated and dried, and then powdered to give 70 to 97 parts of vinyl chloride resin. On the other hand, 30 to 3 parts are compounded by a usual method to prepare the resin composition of the present invention.

When the amount of the graft copolymer used is less than 3 parts,
The degree of improvement in impact strength becomes extremely small, and when it exceeds 30 parts, the transparency and impact resistance of the vinyl chloride resin composition are deteriorated.

The vinyl chloride resin is not particularly limited, and is called a so-called vinyl chloride resin such as polyvinyl chloride, a vinyl chloride copolymer having a vinyl chloride content of about 80% or more, and post-chlorinated polyvinyl chloride. You can use anything you like.

The resin composition of the present invention is molded by a method such as an injection molding method, a calendar molding method, a blow molding method,
The molded article has both high impact resistance and good transparency and can be suitably used for applications such as bottles and sheets.

Next, the composition of the present invention will be described in more detail with reference to Examples.

Example 1 200 parts of water, 1.5 parts of sodium oleate, ferrous sulfate (FeSO
₄ / 7H ₂ O) 0.002 parts, ethylenediaminetetraacetic acid / 2Na salt 0.005 parts, formaldehyde sulfo sodium sulfoxide 0.2 parts, tripotassium phosphate 0.2 parts, butadiene 88 parts, styrene 12 parts, divinylbenzene 1.0 part,
0.1 part of diisopropylbenzene hydroperoxide was charged into a polymerization vessel equipped with a stirrer and polymerized at 50 ° C. for 15 hours to obtain a rubber latex (A) having a polymerization conversion rate of 99% and a weight average particle size of 800 Å.

Rubber latex (A) 225 parts (solid content 75 parts), water 60
Parts, 0.002 parts of ferrous sulfate, 0.004 parts of ethylenediaminetetraacetic acid-2Na salt, 0.1 parts of formaldehyde sulfoxylic acid sodium salt and 1.5 parts of potassium chloride are mixed, and at 70 ° C., 1.0 part of divinylbenzene and butyl acrylate are mixed. 1.0 part and cumene hydroperoxide 0.1 part were added and reacted for 1 hour. Then, a mixed solution of 21 parts of styrene, 1.0 part of methyl methacrylate, 3.0 parts of acrylonitrile and 0.1 part of cumene hydroperoxide was continuously added over 4 hours, and after 1 hour of post-polymerization, a graft copolymer latex was obtained.

The obtained graft copolymer terax was coagulated with sulfuric acid, heat-treated, washed, dehydrated and dried to obtain a graft copolymer (resin).

9 parts of the obtained graft copolymer was mixed with 1.2 parts of octyltin mercapto stabilizer, 0.8 parts of glycerin ricinolate, and 0.2 parts of montanic acid ester vinyl chloride resin (average degree of polymerization 700) of 91 parts, and the mixture was heated at 160 ° C. After kneading with a roll for 8 minutes,
Izod impact strength of JIS K 7110 and JIS K 7110 Izod impact strength and JIS K
The light transmittance according to 6714 was measured. The results are shown in Table 1.

Example 2 Water 200 parts, sodium oleate 1.5 parts, ferrous sulfate (FeSO
₄ · 7H ₂ O) 0.002 parts, 0.005 parts of ethylenediamine tetraacetic acid · 2Na salt, 0.2 parts of sodium formaldehyde sulfoxylate, tripotassium 0.2 parts of phosphoric acid, 68 parts of butadiene, 12 parts of styrene, divinylbenzene, 1.0 part of diisopropyl Charge 0.1 part of benzene hydroperoxide into a polymerization vessel equipped with a stirrer and polymerize at 50 ° C for 10 hours.
After confirming that the polymerization conversion rate is 95% or more, 20 parts of butadiene and 0.05 part of disopropylbenzene hydroperoxide are added and polymerized for 7 hours, and a rubber having a weight average particle size of 800Å and a polymerization conversion rate of 99% is added. A latex (B) was obtained.

Using 225 parts of rubber latex (B), a graft copolymer latex was obtained in the same manner as in Example 1, graft copolymerization was performed, and a composition was prepared and evaluated. First result
Shown in the table.

Example 3 Rubber latex (B) 225 parts, water 60 parts, ferrous sulfate 0.0
02 parts, ethylenediamine tetraacetic acid
2Na salt 0.004 parts, formaldehyde sodium sulfoxylate 0.1 parts and potassium chloride 1.5 parts are mixed, and this is 70 ° C.
Then, 1.0 part of divinylbenzene, 1.0 part of butyl acrylate and 0.1 part of cumene hydroperoxide were added and reacted for 1 hour. Next, 9 parts of styrene, 3 parts of acrylonitrile
And 0.05 parts of cumene hydroperoxide were continuously added over 2 hours, and after 30 minutes, 12 parts of styrene, 1.0 part of methyl methacrylate, and 0.005 parts of cumene hydroperoxide were continuously added over 2 hours, and after 1 hour. After the polymerization, a graft copolymer latex was obtained. After that, a graft copolymer was obtained from the latex in the same manner as in Example 1, and a composition was prepared and evaluated. The results are shown in Table 1.

Comparative Example 1 200 parts of water, 1.5 parts of sodium oleate, ferrous sulfate (FeSO
₄ / 7H ₂ O) 0.002 part, ethylenediamine tetraacetic acid / 2Na salt 0.005 part, formaldehyde sulfoxylic acid sodium 0.2 part, tripotassium phosphate 0.2 part, butadiene 77 part, styrene 23 part, divinylbenzene 1.0 part, diisopropyl Charge 0.1 part of benzene hydroperoxide into a polymerization vessel equipped with a stirrer and polymerize at 50 ° C for 15 hours.
A rubber latex (C) having a polymerization conversion rate of 99% and a polymerization average particle diameter of 800Å was obtained.

Rubber latex (C) 180 parts (solid content 60 parts), water 70
Part, 0.002 part of ferrous sulfate, 0.004 part of ethylenediamine tetraacetic acid 2Na salt, 0.1 part of formaldehyde sulfoxylic acid sodium salt and 1.5 parts of potassium chloride, and mixed with this, 20 parts of styrene and 20 parts of methyl methacrylate at 70 ° C. , 0.1 part of cumene hydroperoxide was continuously added over 5 hours. After 1 hour of post-polymerization, a graft copolymer Terrax was obtained. In the same manner as in Example 1, a graft copolymer was prepared from latex and a composition was prepared and evaluated.

The results are shown in Table 1.

Comparative Example 2 225 parts of rubber latex (C) (75 parts of solid content), 60 water
Part, 0.002 part of ferrous sulfate, 0.004 part of ethylenediamine tetraacetic acid 2Na salt, 0.1 part of formaldehyde sulfoxylic acid sodium salt and 1.5 parts of potassium chloride are mixed, and at this temperature 12.5 parts of styrene and 12.5 parts of methyl methacrylate are mixed. , 0.1 part of cumene hydroperoxide was continuously added over 4 hours. After 1 hour of post-polymerization, a graft copolymer latex was obtained. In the same manner as in Example 1, a graft copolymer was prepared from latex and a composition was prepared and evaluated. The results are shown in Table 1.

Comparative Example 3 Rubber latex (C) 257 parts (solid content 85.7 parts), water 50
Parts, 0.002 parts of ferrous sulfate, 0.004 parts of ethylenediamine tetraacetic acid 2Na salt, 0.1 parts of formaldehyde sulfoxylic acid sodium salt and 1.5 parts of potassium chloride are mixed, and at 70 ° C. 7.15 parts of styrene and 7.15 parts of methyl methacrylate. , 0.1 part of cumene hydroperoxide was continuously added over 3 hours. After 1 hour of post-polymerization, a graft copolymer latex was obtained. In the same manner as in Example 1, a graft copolymer was obtained from latex and a composition was prepared and evaluated. The results are shown in Table 1.

Comparative Example 4 Rubber latex (B) 225 parts (solid content 75 parts), water 60
Part, 0.002 part of ferrous sulfate, 0.004 part of ethylenediamine tetraacetic acid 2Na salt, 0.1 part of formaldehyde sulfoxylic acid sodium salt and 1.5 parts of potassium chloride are mixed, and at this temperature 12.5 parts of styrene and 12.5 parts of methyl methacrylate are mixed. , 0.1 part of cumene hydroperoxide was continuously added over 4 hours. After 1 hour of post-polymerization, a graft copolymer latex was obtained. In the same manner as in Example 1, a graft copolymer was obtained from latex and a composition was prepared and evaluated. The results are shown in Table 1.

Comparative Example 5 Rubber latex (B) 225 parts (solid content 75 parts), water 60
Part, 0.002 part of ferrous sulfate, 0.004 part of ethylenediaminetetraacetic acid / 2Na salt, 0.1 part of formaldehyde sulfoxylic acid sodium salt and 1.5 parts of potassium chloride are mixed, and at 70 ° C., 21 parts of styrene and 4 parts of methyl methacrylate are mixed. , 0.1 part of cumene hydroperoxide was continuously added over 4 hours. After 1 hour of post-polymerization, a graft copolymer latex was obtained. In the same manner as in Example 1, a graft copolymer was obtained from latex and a composition was prepared and evaluated. The results are shown in Table 1.

Comparative Example 6 Rubber latex (B) 225 parts (solid content 75 parts), water 60
Parts, ferrous sulfate 0.002 parts, ethylenediamine tetraacetic acid 2Na salt 0.004 parts, formaldehyde sodium sulfoxylate 0.1 parts and potassium chloride 1.5 parts are mixed, and at 70 ° C. styrene 18.75 parts, acrylonitrile 6.25 parts, A mixed solution of 0.1 part of cumene hydroperoxide was continuously added over 4 hours. After 1 hour of post-polymerization, a graft copolymer latex was obtained. In the same manner as in Example 1, a graft copolymer was obtained from latex and a composition was prepared and evaluated. The results are shown in Table 1.

Comparative Example 7 Rubber latex (B) 225 parts (solid content 75 parts), water 60
Parts, 0.002 parts of ferrous sulfate, 0.004 parts of ethylenediamine tetraacetic acid 2Na salt, 0.1 parts of sodium formaldehyde sulfoxylate and 1.5 parts of potassium chloride are mixed, and at 70 ° C., 0.8 parts of divinylbenzene and 0.9 parts of styrene are mixed. Then, 0.3 part of acrylonitrile and 0.1 part of cumene hydroperoxide were added and reacted for 1 hour. After that, 18.75 parts of styrene, 6.25 parts of acrylonitrile, and 0.1 parts of cumene hydroperoxide were continuously added to the mixed solution for 4 hours. After post-polymerization for 1 hour, a graft copolymer latex was obtained. In the same manner as in Example 1, a graft copolymer was prepared from latex and a composition was prepared and evaluated. The results are shown in Table 1.

Comparative Example 8 Rubber latex (B) 225 parts (solid content 75 parts), water 60
Parts, 0.002 parts of ferrous sulfate, 0.004 parts of ethylenediamine tetraacetic acid 2Na salt, 0.1 parts of sodium formaldehyde sulfoxylate and 1.5 parts of potassium chloride are mixed, and at 70 ° C., 1.0 part of divinylbenzene and 0.75 part of styrene are mixed. , 0.25 part of acrylonitrile and 0.1 part of cumene hydroperoxide were added and reacted for 1 hour. After that, 18.75 parts of styrene, 6.25 parts of acrylonitrile,
A mixed solution of cumene hydroperoxide (0.1 part) was continuously added over 4 hours. After post-polymerization for 1 hour, a graft copolymer latex was obtained. In the same manner as in Example 1, a graft copolymer was prepared from latex and a composition was prepared and evaluated. The results are shown in Table 1.

[Effects of the Invention] The composition of the present invention provides a molded product having impact resistance superior to conventional products while maintaining excellent transparency of the vinyl chloride resin.

 ─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-57-212246 (JP, A) JP-A-58-152039 (JP, A) JP-A-57-102940 (JP, A) JP-A-57- 12856 (JP, A) JP-B-46-21942 (JP, B1)

Claims (1)

(57) [Claims] 1. A crosslinkable resin in the presence of 65 to 85 parts by weight of a butadiene-based polymer comprising (A) 82 to 100% by weight of butadiene and 18 to 0% by weight of another vinyl monomer copolymerizable therewith. 0.1 to 3 parts by weight of monomer and at least one of alkyl acrylate and alkyl methacrylate 0
~ 3 parts by weight and reacted to obtain 50 to 95% by weight of an aromatic vinyl monomer, 0.1 to 40% by weight of a vinyl cyanide monomer, and another vinyl monomer copolymerizable therewith. ~ 40
3 to 30 parts by weight of a resin obtained by emulsion polymerization of 35 to 15 parts by weight of a monomer consisting of 1% by weight so that the total amount with a butadiene-based polymer is 100 parts by weight, and (B) a vinyl chloride resin. A vinyl chloride resin composition comprising 97 to 70 parts by weight, which is excellent in impact resistance and transparency.