JPH03255148A - Modifier and vinyl chloride resin composition containing the same - Google Patents

Abstract

PURPOSE:To improve transparency, impact strength, weatherability, and moldability by polymerizing a vinylated Si compd., and alkyl acrylate, and a vinyl monomer in the presence of an aq. dispersion of a specific crosslinked arom. vinyl polymer. CONSTITUTION:An arom. vinyl compd. is copolymerized in emulsion with 0.05-5wt.% vinylated Si compd. of formula I [wherein R1 is H or 1-4C alkyl; R2 is alkyl or formula II (wherein (l) is 1-3; and R3 is 1-4C alkyl); and X is formula III (wherein (m) is 1-3)] to give an aq, dispersion of a crosslinked arom. vinyl copolymer. A 2-8C alkyl acrylate is copolymerized in emulsion with 0.05-8wt.% the vinylated Si compd. in the presence of the dispersion, giving a crosslinked double-layered rubber-chain polymer having a mean particle diameter of 0.05-3mum. 50-20wt.% vinyl monomer is graft-polymerized in the presence of 50-80wt.% said polymer to give a modifier. 97-50 pts.wt. vinyl chloride resin is compound with 3-50 pts.wt. said modifier.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a modifier for vinyl chloride resin, and a modifier containing the same that has excellent transparency, impact resistance, and weather resistance, and also has good processability. The present invention relates to a modifier for vinyl chloride resin compositions and a vinyl chloride resin composition containing the same.

[Conventional technology]

As is well known, a vinyl chloride polymer or at least 70% by weight of vinyl chloride and other polymerizable monomers copolymerizable therewith3
Copolymers with 0% by weight or less (hereinafter referred to as vinyl chloride resins) have good mechanical and chemical properties and are widely used as general-purpose resins, but they are brittle against impact and difficult to process. There are drawbacks such as poor performance, and in order to improve these, various modifications have been extensively investigated. One of the modification methods that is currently widely used is a method of blending ABS, SBR, or MBS with vinyl chloride resin.

The vinyl chloride resin composition obtained by this method can improve the above-mentioned drawbacks, namely impact resistance and processability, but since the rubber component of ABS, SBR or MBS is polybutadiene-based, It had the disadvantage that its weather resistance was significantly inferior due to UV deterioration of double bonds caused by the ingredients, and it could not withstand long-term outdoor use.

On the other hand, as a modifier for vinyl chloride resin suitable for outdoor use, chemically saturated polyacrylic acid alkyl ester is an elastic material with excellent weather resistance, so it is replaced with the conventional polybutadiene rubber component. However, a wide range of methods have been studied in which various crosslinking agents are used in combination. However, Mi
Although the sole material satisfies weather resistance and impact resistance, the reality is that it is significantly inferior in terms of transparency.

In order to improve this transparency, we focused on the refractive index (n,) of the crosslinked rubber backbone polymer, and
-1,590) as a seed and a crosslinked two-layer rubber backbone polymer with a low refractive index polyacrylic acid ester (no -1,474) as an outer shell, a hard vinyl chloride resin with a refractive index (n = 1.537) is known. For example, in JP-A No. 47-43086, a crosslinked two-layer rubber backbone polymer using diethylene glycol diacrylate, allyl methacrylate, etc. containing at least two vinylidene groups in one molecule as a crosslinking agent, and vinyl chloride monomer The resin obtained by emulsion graft polymerization of the body was also
In JP 79389, methyl methacrylate, methyl methacrylate, Next, a resin in which an aromatic vinyl compound is subjected to emulsion graft polymerization in at least two layers is disclosed. Compositions made by blending resins using these cross-linked two-layer rubber backbone polymers with vinyl chloride resins have certainly improved transparency and achieved certain results, but they contain hard polystyrene resins in the seeds. Even when the particle size is controlled to be appropriate for impact absorption, it is still possible to obtain satisfactory impact resistance, perhaps because the crosslinking agent used does not fully perform its function. It's hard to say.

[Problem to be solved by the invention]

The present invention aims to provide a modifier that provides a vinyl chloride resin composition that practically satisfies transparency and impact resistance and has good processability, and a vinyl chloride resin composition containing the same. be.

[Means to solve the problem]

The present invention emulsifies a vinyl group-containing silicon compound and an acrylic acid alkyl ester (B) in the presence of an aqueous dispersion of an aromatic vinyl compound crosslinked polymer (A) obtained by copolymerizing a vinyl group-containing silicon compound. Provides a vinyl chloride resin modifier comprising a vinyl graft polymer obtained by polymerization and then graft polymerization of a vinyl monomer (C), and a vinyl chloride resin composition containing the same. It is.

Aromatic vinyl compound crosslinked polymer (
A) The aqueous dispersion can be obtained by a conventional emulsion polymerization method.

Examples of the monomer used in this polymer include aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, bromostyrene, and vinyl rubber. These monomers can be used alone or in combination.

Moreover, the aromatic vinyl compound-based crosslinked polymer (A) of the present invention
As a vinyl group-containing organosilicon compound as a crosslinking agent essential for obtaining
In formula C, R1 is H or an alkyl group having 1 to 4 carbon atoms, R2 is an alkyl group having 1 to 4 carbon atoms, or Cn H1*
OR3 (R2 is an alkyl group having 1 to 4 carbon atoms, l is 1
(an integer of 1 to 3), 1

Examples of the silicon compound include vinyltrimethoxysilane CHz=CH5i(OCHs)i, vinyltriethoxysilane CHz=CHSt(OCJs)3
, vinyltris(2-methoxyethoxy)silane CHz
= CHSi (OCJaOCH3): l, vinyltributoxide Hi silane CL = C1l Si (0-CCH3)
Examples include, but are not limited to, s, r-methacrylic Hz ruoxypropyltrimethoxysilane C1,=C-C-0→CH mountain 5i (OCH:+)*. Further, these organosilicon compounds may be used alone or in combination, and may be used in combination with other compounds such as divinylbenzene, mono- or polyethylene glycol dimethacrylate, C5-
It may be used in combination with common crosslinking agents such as hexadiene, 1,9-decadiene, and 113-tetradecadiene. The silicon compound is preferably copolymerized in the aromatic vinyl compound crosslinked polymer in an amount of 0.05 to 5% by weight, more preferably 0.1 to 2% by weight.

Within this range, a modifier that provides a vinyl chloride resin composition with excellent impact resistance, transparency, etc. is produced.

The aromatic vinyl compound crosslinked polymer of the present invention is obtained by ordinary emulsion polymerization, and the emulsifiers include potassium oleate, sodium oleate, sodium dodecylbenzenesulfonate, sodium alkyl diphenyl ether disulfonate, and polyoxyethylene alkyl ether sulfate. Anionic emulsifiers such as soda, naphthalene sulfonic acid formalin condensate, nonionic emulsifiers such as polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene propylene block polymer,
Known surfactants such as cationic emulsifiers such as laurylamine acetate can be used.

In addition to known polymerization initiators such as persulfates and oxidation-reduction (redox) initiators, chain transfer agents, PU regulators, etc. for controlling the degree of polymerization can also be added as necessary. In the production of a crosslinking agent consisting of an aromatic vinyl compound monomer and a vinyl group-containing silicon compound as essential components, the entire amount may be charged at once, or a part or the entire amount may be added continuously or intermittently while polymerizing. You may do so.

Next, in the presence of an aqueous dispersion of an aromatic vinyl compound crosslinked polymer using the vinyl group-containing silicon compound of the present invention as a crosslinking agent, a mixture of the vinyl group-containing silicon compound of the present invention and an acrylic acid alkyl ester is prepared. is added and emulsion polymerized. In this case, the vinyl group-containing silicon compound is added in an amount of preferably 0.05 to 8% by weight, preferably 0.1 to 5% by weight, in the mixture. When the amount used is within this range, a modifier that provides a vinyl chloride resin composition with particularly excellent impact resistance can be obtained. Further, these vinyl group-containing silicon compounds may be used alone or in combination, or may be used in combination with the above-mentioned ordinary crosslinking agents.

In the acrylic acid alkyl ester, the alkyl group has 2 to 8 carbon atoms, and the alkyl group may be linear or branched. Examples thereof include ethyl acrylate, propyl acrylate, n-butyl acrylate, pentyl acrylate, hexyl acrylate, n-octyl acrylate, and 2-ethylhexyl acrylate. These monomers can be used alone or in combination. Further, 0 to 30% by weight of these acrylic acid alkyl esters may be substituted with other copolymerizable monomers.

Examples of other copolymerizable monomers include styrene, vinyltoluene, α-methylstyrene, chlorostyrene,
Aromatic vinyl compounds such as bromostyrene and vinyl carbazole; conjugated diolefins such as 1,3-butadiene, isoprene and chlorobrene; methacrylic acid alkyl esters such as methyl methacrylate and ethyl methacrylate;
Acrylic acid or methacrylic acid derivatives such as acrylic acid, methacrylic acid, glycidyl acrylate and glycidyl methacrylate; vinyl cyanide compounds such as acrylonitrile and methacrylaterile; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; halogens such as vinyl chloride and vinyl bromide. Vinylitine halides such as vinyl chloride, vinylidene chloride, and vinylidene bromide, and vinyl esters such as vinyl acetate and vinyl propionate can be used.

In the presence of an aqueous dispersion of an aromatic vinyl compound crosslinked polymer,
Emulsion polymerization of a mixture of a vinyl group-containing silicon compound and an acrylic acid alkyl ester as essential components is carried out by a normal emulsion polymerization method, and in addition, known polymerization initiators such as persulfates and redox systems, and new particles if necessary are used. If necessary, emulsifiers, chain transfer agents, pH adjusters, etc. may be added in minimum amounts to the extent that no .

In this way, a crosslinked polymer made of an aromatic vinyl compound and a vinyl group-containing silicon compound as a crosslinking agent is used as a seed, and an acrylic crosslinked rubber polymer made of a vinyl group-containing silicon compound and an acrylic acid alkyl ester is used as a crosslinking agent. A so-called crosslinked two-layer rubber backbone polymer having the outer shell formed by the coalescence is obtained. The composition of this crosslinked two-layer rubber backbone polymer is preferably such that the aromatic vinyl compound is 25 to 60% by weight and the acrylic acid alkyl ester is 75 to 40% by weight.

When the amounts of the aromatic vinyl compound and the acrylic acid alkyl ester are within this range, a vinyl chloride resin composition with satisfactory transparency and impact resistance can be obtained. Also,
Even if the ratio of the aromatic vinyl compound and the acrylic acid alkyl ester is within this range, if these two are simply copolymerized randomly instead of in two layers, the transparency of the composition with the vinyl chloride resin will be improved. However, the impact resistance is poor, and the seeds and outer shell of this cross-linked two-layer rubber backbone polymer were replaced, that is, the seeds were replaced with an acrylic cross-linked rubber polymer, and
When aromatic vinyl crosslinked polymer is placed in the outer shell,
The result is that the transparency is very poor compared to the case of the present invention. Furthermore, the modifier of the present invention using this crosslinked two-layer rubber backbone polymer has problems in all aspects such as transparency, impact resistance, weather resistance, and processability when a known crosslinking agent is used. It is not possible to impart excellent performance to vinyl chloride resin,
This is achieved only by using a vinyl group-containing silicon compound as a crosslinking agent.

The average particle diameter of the crosslinked two-layer rubber backbone polymer is also an important factor, and is preferably in the range of 0.05 to 0.3 μm.

When the average particle diameter of the two-layer rubber backbone polymer is within the range that allows crosslinking, a vinyl chloride resin composition with excellent transparency, impact resistance, and processability can be obtained.

In order to obtain compatibility with the vinyl chloride resin, the modifier made of the graft copolymer of the present invention is a crosslinked two-layer rubber backbone which is crosslinked with a vinyl group-containing silicon compound as a crosslinking agent as an essential component. It is produced by graft polymerization (C) of vinyl monomers in the presence of an aqueous dispersion of the polymer.

The graft components for achieving this compatibility are preferably 100 to 0% by weight of an alkyl methacrylate having 1 to 4 carbon atoms and 0 to 9% by weight of an aromatic vinyl compound.
0% by weight, vinyl cyanide compound from 0 to 50% by weight, or monomers copolymerizable with these monomers from O to 50% by weight.
It can be used in an amount of about 20% by weight. Furthermore, by using a crosslinking agent copolymerizable with the graft component, crosslinking can be carried out while performing graft polymerization. The crosslinking agent for this purpose may be the aforementioned vinyl group-containing silicon compound or the aforementioned ordinary crosslinking agent that can be copolymerized into one molecule.

The amount used is 0 to 5% by weight based on the graft component. If it exceeds 5% by weight, the graft component will be too crosslinked and its compatibility with the vinyl chloride resin will decrease, making it difficult to develop impact resistance and weather resistance.

The methacrylic acid alkyl ester as a graft component preferably has an alkyl group having 1 to 4 carbon atoms, and may be linear or branched. For example, methyl methacrylate,
Examples include ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, butyl methacrylate, and t-butyl methacrylate, which can be used alone or in combination.

Further, examples of aromatic vinyl compounds include styrene, vinyltoluene, α-methylstyrene, chlorostyrene, bromustyrene, vinylcarbazole, etc., and examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.

Monomers that can be copolymerized with these include acrylic acid containing a single vinyl group or vinylidene group, acrylic ester, acrylamide, methacrylic acid, and other organic residues other than those in which the alkyl group has 1 to 4 carbon atoms. methacrylic acid ester, methacrylamide, alkyl vinyl ether,
Alkyl vinyl ester, N-phenylmaleimide, N
-N-substituted maleimides such as cyclohexylmaleimide and the like.

In addition, as the vinyl monomer to be graft-polymerized,
Vinyl chloride can be used alone or mixed with 0 to 30% by weight of other monomers copolymerizable with vinyl chloride.

Graft polymerization refers to adding the entire amount of the above-mentioned graft component, if necessary a crosslinking agent, and a mixture of these graft components to the aqueous dispersion liquid at once, or continuously or intermittently, in whole amount or a part thereof. The polymerization was completed.

Furthermore, the resulting graft polymer may be used by uniformly mixing all of the components, or may be graft polymerized in two or more stages while changing the composition within the above component range that satisfies compatibility. From the combined aqueous dispersion, the polymer powder is recovered by spray drying, or the polymer powder is recovered by salting out, coagulating, filtering, washing with water, and drying. At this time, it can be co-coagulated with an aqueous dispersion of vinyl chloride resin, and known antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, etc. can also be added.

The graft copolymer obtained by graft-polymerizing a vinyl monomer onto a cross-linked two-layer rubber backbone polymer as a modifier of the present invention is a graft copolymer obtained by graft-polymerizing a vinyl monomer onto a cross-linked two-layer rubber backbone polymer. Preferably, the amount is 50 to 20 parts by weight. When the proportions of the crosslinked two-layer rubber backbone polymer and the vinyl monomer are within the above range, the effect of improving the transparency and impact resistance of the vinyl chloride resin composition is large, and powders such as acid precipitation and salting out It can be uniformly mixed with vinyl chloride resin without clumping during the drying and drying stages.

The vinyl chloride resin of the present invention includes a normal vinyl chloride resin, preferably a vinyl chloride polymer and/or at least 70% vinyl chloride and other polymerizable monomers copolymerizable therewith. It is a copolymer with 0 to 30% by weight.

Other polymerizable monomers include, for example, vinylidene halides such as vinylidene chloride and vinylidene bromide; vinyl acetate;
Examples include vinyl esters such as vinyl propionate; alkyl acrylates such as methyl acrylate; alkyl methacrylates such as methyl methacrylate; aromatic vinyl compounds such as styrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. .

These monomers can be used alone or in combination with vinyl chloride.

The vinyl chloride resin composition of the present invention preferably comprises 97 to 50 parts by weight of a vinyl chloride resin and 3 to 50 parts by weight of a modifier made of a graft copolymer. If the amount of the graft copolymer is less than 3 parts by weight, it is difficult to develop impact resistance;
If the amount is more than 0 parts by weight, the properties of the vinyl chloride resin will be lost and there will be no point in adding it.

The graft polymer and the vinyl chloride resin, which are the modifiers of the present invention, are mixed using a known mixer such as a Henschel mixer, ribbon blender, roll mill, Banbury mixer, etc., and then injection molding machine, extrusion The molding process can be performed using a known processing machine such as a machine.

At that time, conventionally known heat stabilizers, ultraviolet absorbers, light stabilizers, lubricants, fillers, processing aids, pigments, antistatic agents, etc. can be optionally added as necessary. In addition, the modifier made of the graft polymer of the present invention may further contain other polymers that are compatible with the vinyl chloride resin, such as ethylene/vinyl acetate copolymers, ethylene/acrylic acid ester copolymers, and these. Graft copolymers of copolymers and vinyl chloride, styrene/acrylonitrile copolymers, ABS resins, MBS resins, acrylonitrile/butadiene coaggregates, chlorinated polyethylene, etc., and vinyl chloride resins together with plasticizers. It is also possible to mix them.

A crosslinked two-layer rubber trunk polymer is produced in which the specific vinyl group-containing organosilicon compound of the present invention is used as an essential crosslinking agent, and the seed is an aromatic vinyl compound crosslinked polymer and the outer shell is an acrylic crosslinked rubber polymer. The vinyl chloride resin composition using the graft polymer used as a modifier has a transparency comparable to that of polyvinyl chloride resin alone without using a modifier, and has significantly superior impact resistance and processability. There is.

Furthermore, compared to the case where the specific organosilicon compound of the present invention is not used as an essential crosslinking agent, the transparency is the same or higher,
Workability 1: It has good surface properties and whitening property when folded, and has excellent impact resistance including weather resistance.

Furthermore, since the resin of the present invention has fundamentally improved weather resistance compared to commercially available MBS resins, it can be used for outdoor applications such as agricultural materials, industrial parts, and construction materials, such as PVC window frames, sizing materials, It can be used for industrial hard plates, pipes, corrugated plates with improved transparency, etc.

〔Example〕

Next, the present invention will be specifically explained with examples, but the present invention is not limited thereto. In addition,
In the examples, "parts" and "%" do not represent "parts by weight J" or "% by weight."

Example 1 (A) 875 parts of ion-exchanged water was charged into a 21 stainless steel flask equipped with a stirrer in a nitrogen gas flow, heated to 85°C, and then 6.0 parts of sodium dodecylbenzenesulfonate was added. was added and dissolved. While maintaining the temperature in the system at 85°C, a mixed solution of 270 parts of styrene monomer and 2.7 parts of vinyltris(2-methoxyethoxy)silane and an aqueous solution of 1.8 parts of potassium persulfate dissolved in 60 parts of ion-exchanged water were added in parallel. Then, the polymerization was proceeded by dropping the solution over a period of 3 hours. Polymerization was continued for an additional 2 hours at a temperature of 85°C to complete the reaction. Polymerization rate is 98
% or more. The average particle diameter of this aromatic vinyl compound crosslinked polymer is 0.110 μ steel, and the gel content is 90.5%.
Met. The average particle diameter was measured using Coulter N, manufactured by Coulter Co., Ltd., using scattered light spectroscopy using He-Ne laser light.
It was measured using a Type 4 submicron particle analyzer. The gel content was determined by drying an aqueous dispersion of an aromatic vinyl compound-based crosslinked polymer on a petri dish, immersing a portion (Wog) in chloroform at 30°C for 48 hours, and drying the swollen sample completely. The weight (Wag) was measured and calculated using the following formula.

O B) Addition Rubber Person 〇 ″ In the presence of the aqueous dispersion of the aromatic vinyl compound-based crosslinked polymer thus obtained, 330 parts of n-butyl acrylate and vinyl tris( A mixed solution of 3.3 parts of 2-methoxyethoxy)silane and an aqueous solution of 1.8 parts of potassium persulfate dissolved in 60 parts of ion-exchanged water were simultaneously added dropwise over 3 hours to proceed with polymerization.85
Polymerization was continued for an additional 2 hours at a temperature of 0.degree. C. to complete the reaction. The polymerization rate was 98% or more. Also, the average particle diameter is 0
．． 140 μm, substantially no new particles were observed, and aromatic vinyl compound-based crosslinked polymer was used as seed.
A crosslinked two-layer rubber backbone polymer having an outer shell made of an acrylic crosslinked rubber polymer composed of n-butyl acrylate was obtained. The gel content of this crosslinked two-layer rubber backbone polymer was measured to be 92.5% in the same manner as above.

(Boots as C) 558 parts of the aqueous dispersion containing the crosslinked two-layer rubber backbone polymer obtained in (B) above (polymer solid content 210 parts) and 185 parts of ion-exchanged water were mixed in a nitrogen stream. The mixture was placed in a 1.5A stainless steel flask equipped with a stirrer, and heated and maintained at 85°C.

Next, 45 parts of methyl methacrylate and 9 parts of ion-exchanged water
An aqueous solution of 0.45 parts of potassium persulfate dissolved in 0.0 parts of potassium persulfate was added dropwise in parallel over a period of 2 hours to advance the polymerization, and the polymerization was further maintained at 85° C. for a working time to complete the polymerization. Subsequently, at the same temperature, an aqueous solution of 0.45 parts of potassium persulfate dissolved in 45 parts of styrene and 90 parts of ion-exchanged water was added dropwise in parallel over 2 hours to polymerize, and the temperature was further maintained for 1 hour to continue polymerization. Completed it. The polymerization rate was 97% or more, and the average particle diameter of the obtained graft polymer was 0.160 μm. Note that substantially no new particles were observed.

Calcium chloride was added to the aqueous dispersion of the graft polymer produced in this way, followed by salting out coagulation, dehydration, washing with water, and drying to obtain a powdery graft polymer as a modifier of the present invention. Ta.

(D) Vinyl Part 11 The blend shown in Table 11 was kneaded for 5 minutes using a 6-inch test roll adjusted to 190°C to obtain a vinyl chloride resin composition. This M
i-kai success press temperature 190℃, press pressure 150kg/
The physical properties of the U acid product were measured by molding it into a triple-thick press sheet using csA. The results are shown in Table 2. Table 2 also shows the measurement results when no modifier was used.

Note that the physical properties of the composition were measured by the following method.

- Transparency: Total light transmittance and haze value were measured using an integrating sphere haze meter according to JIS K 6714.

- Impact resistance: Notched Izot impact strength was measured at 0°C and 23°C according to ASTM D-256-56.

・Weather resistance: 40 according to Sunshine Weatherometer
Accelerated exposure tests for 0 hours and i,ooo hours were conducted, and the above-mentioned notched Izot impact strength was measured at 23°C.

- Processability: When the graft polymer mixture was kneaded using a 6-inch test roll, the degree of cohesion of the mixture was observed.

- Surface properties The presence or absence of unmelted spots (finshuai) and gloss were observed as the surface condition of the nibbles sheet.

- Whitening property on bending: A 0.5-press sheet was separately prepared under the above conditions, and this press sheet was bent to observe the degree of whitening at the folded portion.

Example 2 The same procedure as in Example 1 (A) and (B) was repeated except that 2-acrylic acid was used instead of n-butyl acrylate in B).
Using the same amount of ethylhexyl, average particle size 0.135
A crosslinked two-layer rubber backbone polymer with a gel content of 92.0% was obtained. Next, the same amount of this aqueous dispersion as in (C) of Example 1 and ion-exchanged water were charged into a flask, and 0.0% of potassium persulfate was dissolved in 90 parts of methyl methacrylate and 90 parts of ion-exchanged water at a temperature of 85°C. Polymerization was proceeded by dropping 9 parts of an aqueous solution in parallel over a period of 3 hours, and the polymerization was completed by maintaining the same temperature for another 1 hour to obtain a graft polymer with an average particle size of 0.150 μm. In addition, the polymerization rate was 98% or more in all the above steps. Subsequently, a test piece of a vinyl chloride resin composition was prepared using the graft polymer powder of the present invention obtained in the same manner as in Example 1, and its physical properties were measured.

The results are shown in Table 2.

Example 3 A crosslinked two-layer rubber backbone polymer was obtained by operating in the same manner as in Example 1 (A> and (B)).
This aqueous dispersion 558 was added to a cnl 2e autoclave.
(polymer solid content: 210 parts), 200 parts of ion exchange water,
Potassium persulfate 0645 dissolved in 90 parts of ion-exchanged water
0.06 part of dipotassium hydrogen phosphate, and 30 parts of liquefied vinyl chloride were charged, and the reaction system was heated to 75° C. and maintained at this temperature.

After the pressure decreased to 0.4 kg/cat, the reactor and contents were rapidly cooled and the remaining vinyl chloride monomer was discharged from the system. The obtained graft polymer had an average particle diameter of 0.155 μm, and no new particles were observed to be formed. Subsequently, a graft polymer powder was obtained in the same manner as in Example 1, and a test piece of a vinyl chloride resin was prepared to measure its physical properties.

The results are shown in Table 2.

Comparative Example 1 A graft polymer powder was obtained in the same manner as in Example 1, except that the crosslinking agent used during the operations (A> and (B) in Example 1 was replaced with the same amount of allyl methacrylate, and then chlorinated Test pieces of the vinyl resin composition were prepared and their physical properties were measured.The results are shown in Table 2.

Comparative Example 2 A crosslinked two-layer rubber backbone polymer was obtained by replacing the crosslinking agent used in (A) and (B) of Example 1 with the same amount of allyl methacrylate, and then operated in the same manner as in Example 3. Graph I polymer powder and granules containing vinyl chloride in graphs 1 to 1 were obtained. Subsequently, a test piece of the vinyl chloride resin composition was prepared in the same manner as in Example 1, and its physical properties were measured. The results are shown in Table 2.

/ / / / / 2/ / / Example 4 and Comparative Example 3 In (A) and (B) of Example 1, the type and amount of the crosslinking agent used were changed as shown in Table 3. A crosslinked two-layer rubber backbone polymer was obtained. Thereafter, in the same manner as in Example 1, a vinyl chloride resin assembly was obtained.

Table 3 shows the gel content of the above-mentioned backbone polymer and the measured physical properties of the vinyl chloride resin composition.

Comparative Example 4 The same procedure as in Example 1 (A) and (B) was carried out, except that styrene and n-butyl acrylate were copolymerized or
Alternatively, butyl acrylate was substituted for the seeds and styrene was substituted for the outer shell and polymerization was performed to obtain two types of crosslinked rubber trunk polymers. The transparency and impact resistance of a vinyl chloride resin composition produced in the same manner as in Example 1 were measured. The results are shown in Table 4. Note that Table 4 also shows the results of Example 1.

Noah' Example 5 and Comparative Example 5 In Example 1 (A) and (B), the composition ratios of styrene and n-butyl acrylate as monomers were changed as shown in Table 5, A crosslinked two-layer rubber backbone polymer was produced, and the following procedure was carried out in the same manner as in Example 1. The transparency and impact resistance of the obtained vinyl chloride resin composition were measured. The results are shown in Table 5. Table 5 also shows the results of Example 1.

/ / /' Example 6 and Comparative Example 6 In Example 2, however, the composition ratio of the crosslinked two-layer rubber backbone polymer and methyl methacrylate, which is a monomer to be graft-polymerized, was as shown in Table 6. A graft polymer was produced by varying the conditions, and the transparency and impact resistance of the obtained vinyl chloride resin Mi were measured in the same manner as in Example 2.

The results are shown in Table 6. In addition, Table 6 shows Example 2.
The results are also listed.

Example 7 and Comparative Example 7 Graft polymers of Examples 1.2 and 3, Comparative Examples 1 and 2, MBS resin which is a commercially available impact modifier for vinyl chloride resins, and polyvinyl chloride resin without adding a modifier Weather resistance was measured for each individual sample, and the results are shown in Table 7.

〔Effect of the invention〕

The present invention is a modifier that provides a vinyl chloride resin composition that has practically satisfactory transparency and 11J impact resistance and has good processability, and a vinyl chloride resin composition containing the same.

Claims (1)

[Claims] 1. A vinyl group-containing silicon compound and an acrylic acid alkyl ester ( A modifier for vinyl chloride resins comprising a vinyl graft polymer obtained by emulsion polymerization of B) and then graft polymerization of vinyl monomer (C). 2. The vinyl group-containing silicon compound has the general formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] [In the formula, R_1 is H or an alkyl group having 1 to 4 carbon atoms,
R_2 is an alkyl group having 1 to 4 carbon atoms or C_2H_2_
l-O-R_3 (where l is an integer from 1 to 3, R_3 represents an alkyl group having 1 to 4 carbon atoms), )
, n represents 0 or 1]. The modifier according to claim 1. 3. The amount of vinyl group-containing silicon compound copolymerized into the aromatic vinyl compound-based crosslinked polymer (A) is 0 with respect to the polymer.
．． 2. The modifier according to claim 1, wherein the modifier is 0.05 to 5% by weight. 4. The modifier according to claim 1, wherein the vinyl group-containing silicon compound and the vinyl group-containing silicon compound in the acrylic acid alkyl ester (B) are 0.05 to 8% by weight. 5. A vinyl chloride resin composition containing the modifier according to claim 1, 2 or 3.