JPH03106956A - Modifier and vinyl chloride resin composition containing same - Google Patents

Abstract

PURPOSE:To obtain a vinyl chloride resin compsn. excellent in the impact strength, weathterability, processability, and transparency by graft polymerizing a vinyl monomer in the presence of an aq. dispersion of a specific crosslinked acrylic rubber backbone polymer. CONSTITUTION:An alkyl acrylate, if necessary with another copolymerizable monomer, is emulsion polymerized in water in the presence of a crosslinker comprising a vinylated silicon compd. of formula I [wherein R1 H or 1-4C alkyl; R2 is 1-4C alkyl or a group of formula II (wherein l is 1-3; and R3 is 1-4C alkyl); X is a group of formula III (wherein m is 1-3); and n is 0 or 1] and an emulsifier to give an aq. dispersion of a crosslinked acrylic rubber backbone polymer with a mean particle diameter of 0.05-0.3mum. In the presence of the resulting backbone polymer, a vinyl monomer is graft polymerized to give a vinylic graft polymer useful as a modifier for vinyl chloride resin.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a modifier and, by containing the same, a modifier that has excellent impact resistance, weather resistance, good processability, and improved transparency. Concerning vinyl chloride resin compositions. [Prior art and its problems] As is well known, a vinyl chloride polymer or at least 70% by weight of vinyl chloride and other polymerizable monomers copolymerizable therewith 3
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 impacts and have poor processability. There are drawbacks such as poor performance, and in order to improve these, various modifications have been extensively investigated. One of the most commonly used modification methods at present 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, Due to the deterioration of the double bond caused by putadiene by ultraviolet rays, the weather resistance was significantly inferior, and it had the disadvantage that it could not withstand long-term outdoor use.

On the other hand, since chemically saturated polyacrylic acid alkyl ester is an elastic material with excellent weather resistance, it can be used as a modifier for vinyl chloride resins suitable for outdoor use. Replacement methods are being widely considered. For example, British Patent No. 927,821 discloses the presence of acrylic acid alkyl ester polymers with crosslinking agents such as divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate (DAP) in amounts up to 1.5% by weight. Below is a copolymer obtained by graft polymerizing a monomer or a monomer mixture of a methacrylic acid alkyl ester, an aromatic vinyl compound, and a vinyl cyanide compound.
Although it is described that it is mixed with a vinyl chloride resin, it is not described whether it improves impact resistance and also has excellent weather resistance.

Further, in US Pat. No. 3,655,825, 0.1 to 5% by weight of di- or tri-(meth)acrylate of a polyhydric alcohol is used as a crosslinking agent. Since then, with regard to the above-mentioned graft copolymers, various types of crosslinking monomers have been extensively investigated, and certain results have been obtained. However, the current situation is that vinyl chloride resins have not yet satisfied all of the body impact resistance, weather resistance, processability, and transparency in a well-balanced manner.

In particular, there are still problems with impact strength reduction and processability after UV degradation and at low temperatures, and improvements in these areas are desired by the market. [Means for Solving the Problems] In view of the current situation, the present inventors have conducted extensive research on modifiers made of acrylic acid alkyl ester copolymers, and have found that a specific modifier has excellent impact resistance, The inventors have discovered that it is possible to provide a vinyl chloride resin that has excellent weather resistance, good processability, and improved transparency, and has thus arrived at the present invention. That is, the present invention involves graft polymerizing (B) a vinyl monomer in the presence of (A) an aqueous dispersion of an acrylic crosslinked rubber backbone polymer using a vinyl group-containing silicon compound as a crosslinking agent. The present invention provides a vinyl chloride resin modifier made of the obtained vinyl graft polymer and a vinyl chloride resin composite bottom containing the modifier. [Structure] The aqueous dispersion of a crosslinked rubber backbone polymer (usually referred to as acrylic rubber) used to produce the graft copolymer that is the modifier of the present invention can be obtained by a conventional emulsion polymerization method.
The monomer used for this polymer consists of an acrylic acid alkyl ester and other monomers if necessary, and preferably the alkyl group has 2 to 8 carbon atoms, and the alkyl group may be linear or It may be branched. Examples include ethyl acrylate, probyl acrylate, n-butyl acrylate,
Bentyl acrylate, hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, and the like. These monomers can be used alone or in combination. Further, 10 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,
Aromatic vinyl compounds such as chlorostyrene, furomostyrene, and vinyl carbazole; conjugated diolefins such as 1,3-butadiene, isoprene, and chloroprene; alkyl methacrylates such as methyl methacrylate and ethyl methacrylate; acrylic acid, methacrylic acid, and glycidyl acrylate. , acrylic acid or methacrylic acid derivatives such as glycidyl methacrylate, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, vinyl ethers such as methyl vinyl ether and butyl vinyl ether, vinyl halides such as vinyl chloride and vinyl bromide, vinylidene chloride, and bromide. Vinylidene chloride, such as vinylidene,
Vinyl esters such as vinyl acetate and vinyl propionate can be used. Moreover, the crosslinked rubber backbone polymer (A) of the present invention
As a vinyl group-containing organosilicon compound as a crosslinking agent essential for obtaining the general formula [I] R, ct+t-c-<χ+rSi(ORz)s (in the formula R+
is H or an alkyl group having 1 to 4 carbon atoms, Rt is an alkyl group having 1 to 4 carbon atoms, or CrHzt O Rz
(Rs is an alkyl group having 1 to 4 carbon atoms, 1 is an integer of 1 to 3), X is 0 11 C O C@Hzs (m is an integer of 1 to 3), n is O or 1] is preferable. As the silicon compound, for example, vinyltrimethoxysilane CH
z-CH St(OCRs)s, vinyltriethoxysilane CHz=CI{ Si(OCJs)s,
Vinyltris(2-methoxyethoxy)silane CH寞=
CH Si(O CzHnOCHs)s, vinyltributoxyClh silane CHz=CH St(OC CH3)
! , γ-Meta CH3 Chryloxypropyltrimethoxysilane CII3 C■t=C -C -0{CHx+TSi (OCHs)
+ and the like, but are not limited to these. 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, 1.9-decadiene, 1,5-hexadiene, 1.13 -Can be used in combination with common crosslinking agents such as tetradecadiene. The silicon compound is preferably present in the crosslinked rubber backbone polymer in an amount of 0.1 to 10% by weight, more preferably 0.1 to 10% by weight. It must be contained in an amount of 2-8% by weight.

If it is less than this range, there will be a shortage of crosslinking and grafting active sites, resulting in insufficient impact resistance, and if it exceeds this range, there will be too much crosslinking, resulting in a decrease in impact resistance.

The crosslinked rubber backbone 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 sodium polyoxyethylene alkyl ether sulfate. , anionic emulsifiers such as naphthalene sulfonic acid formalin condensate, nonionic emulsifiers such as polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene brobylene block polymer, and cationic emulsifiers such as laurylamine acetate. Surfactants can be used. In addition to known polymerization initiators such as peroxides and oxidation-reduction (redox) initiators, chain transfer agents and pi regulators for controlling the degree of polymerization can also be added as necessary. A certain crosslinking agent consisting of an acrylic acid alkyl ester and an organosilicon compound as essential components may be added in its entirety at once, or may be polymerized while being added in part or in its entirety continuously or intermittently. The average particle size of the crosslinked rubber backbone polymer in the aqueous dispersion thus obtained is suitably in the range of 0.05 to 0.3 μm. If the average particle diameter is smaller than 0.05μ, the effect of increasing the impact resistance of the obtained vinyl chloride resin composition is small. Therefore, in such cases, it is desirable to increase the particle size using a known aggregation method before or during graft polymerization. If the average particle diameter is larger than 0.3 μm, dispersion into the vinyl chloride resin tends to be insufficient, resulting in a decrease in processability and impact resistance of the resulting vinyl chloride resin composition. Graft polymerization is carried out by adding a polymerization initiator, if necessary, an emulsifier, a chain transfer agent, a pHJ moderating agent, and others in the presence of the aqueous dispersion of the crosslinked rubber backbone polymer obtained in this way, and carrying out conventional emulsion polymerization. This can be done by the following method.

In order to obtain compatibility with the vinyl chloride resin, the modifier made of the graft copolymer of the present invention is an aqueous base polymer of crosslinked rubber that is crosslinked using a vinyl group-containing silicon compound as a crosslinking agent. It is produced by graft polymerization in the presence of a dispersion. In order to achieve this compatibility, it is preferable that the alkyl group has 1 to 4 carbon atoms.
A monomer consisting of 0 to 0% by weight of methacrylic acid alkyl ester, 0 to 90% by weight of an aromatic vinyl compound, and 0 to 50% by weight of a vinyl cyanide compound, or a monomer copolymerizable with these monomers. It can be used in an amount of about 20% by weight. Furthermore, it is also possible to carry out crosslinking while carrying out graft polymerization by using a crosslinking agent that can be copolymerized to some extent. The crosslinking agent for this purpose may be the above-mentioned organosilicon compound or the above-mentioned 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%, the graft content will be too cross-linked and the compatibility with the vinyl chloride resin will decrease, making it difficult to develop impact resistance and weather resistance. The methacrylic acid alkyl ester used as the 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, probyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, and the like, which can be used alone or in combination.

Further, examples of aromatic vinyl compounds include styrene, vinyltoluene, α-methylstyrene, chlorostyrene, promustyrene, vinylcarbazole, etc., and examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile. Monomers that can be copolymerized with these include acrylic acid, acrylic ester, acrylamide, methacrylic acid containing a single vinyl group or vinylidene group, 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-phenyl maleigodo, N
- N-substituted maleimides such as cyclohexylmaleimide, etc.

Graft polymerization refers to adding a portion of the above-mentioned graft, if necessary, a crosslinking agent and a mixture of these graft components all at once, or all or a portion thereof continuously or intermittently to the aqueous dispersion. was added to complete the polymerization.

Furthermore, all of them may be used as a homogeneous mixture, or graft polymerization may be carried out in two or more stages while changing the composition within the above-mentioned range that satisfies compatibility. The resulting aqueous dispersion of the graft polymer is spray-dried to recover the polymer powder, or is salted out, coagulated, filtered, washed with water, and then dried to recover the polymer powder. 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 as a modifier of the present invention is a polymer 2 graft polymerized to 50 to 80 parts by weight of a crosslinked rubber backbone polymer.
From 0 to 50 parts by weight. If the crosslinked rubber backbone polymer is less than 50 parts by weight, the effect of improving the impact resistance of the resulting vinyl chloride resin composite sole is small, and if it is more than 80 parts by weight, acid precipitation, salting out, etc. may occur during powdering and drying stages. It turned into lumps,
It becomes impossible to mix uniformly with vinyl chloride resin.

The vinyl chloride resin of the present invention includes a normal vinyl chloride resin, preferably a vinyl chloride polymer and/or at least 70% by weight of vinyl chloride and other polymerizable monomers copolymerizable therewith. It is a copolymer with ~30% by weight. Other polymerizable monomers include, for example, vinylidene halides such as vinylidene chloride and vinylidene bromide; vinyl acetate,
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 p-based resin, which are the modifiers of the present invention, are mixed using a known mixer such as a Henschel mixer, a ribbon blender, a roll mill, or a Banbury mixer, and then an injection molding machine, an extrusion The shape can be processed 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 copolymers, chlorinated polyethylene, etc., and vinyl chloride resins together with plasticizers. It is also possible to combine them. [Example] Next, the present invention will be specifically explained using examples.
The present invention is not limited to these. In addition, both "parts" and "%" in the examples refer to "parts by weight J
and "% by weight".

Example 1 (A) The ingredients listed in Table 1 were charged into a 21 stainless steel flask in a nitrogen stream, and the ingredients listed in Table 2 were mixed with the ingredients listed in Table 2 under stirring while maintaining the temperature at 35°C. 14.1 parts corresponding to 5%, and then 0.56 parts of diisobutylbenzene hydroperoxide as a polymerization initiator were charged. After that, the temperature of the reaction system was increased to 40℃.
26, which corresponds to the remaining 95% of the mixed precepts in Table 2.
7. 9 parts of sodium formaldehyde sulfoxylate and 42 parts of an aqueous solution containing 1.6 parts of sodium formaldehyde sulfoxylate were added dropwise in parallel over a period of 3 hours to proceed with polymerization. Table 1 Ion exchange water 960 parts Sodium oleate 6 Disodium ethylenediaminetetraacetate 0.04σ Ferrous sulfate
0.02〃Sodium pyrophosphate 2〃Additionally 2 at a temperature of 40℃
Polymerization was continued for an hour to complete the reaction. The polymerization rate was 98% or more. The average particle diameter of this crosslinked rubber backbone polymer is 0
．． 07 μm, gel content was 91%. The average particle diameter of the crosslinked rubber backbone polymer 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 the crosslinked rubber backbone polymer on a petri dish, and adding a portion (Wag) of it to chloroform for 30 min.
After soaking at ℃ for 48 hours, the sample was dried completely and the weight (
Wag) was measured and calculated using the following formula.

Table 2 n-Butyl acrylate 280 parts The thus obtained aqueous dispersion containing the crosslinked rubber backbone polymer with a solid content of 70 parts was heated and maintained at a temperature of 60°C,
% acetic acid aqueous solution was gradually added to enlarge the particles. The average particle diameter was 0.16 μm. After stabilizing the dispersion by adding 80 parts of a 2% aqueous sodium hydroxide solution, 0.24 part of diisopropylbenzene hydroperoxide was added, followed by 120 parts of methyl methacrylate and 0.8 parts of sodium formaldehyde sulfoxylate.
21 parts of an aqueous solution containing 50% of the total amount was added dropwise in parallel over 4 hours. Polymerization was further continued at a temperature of 60° C. for 2 hours to complete the reaction. The polymerization rate was 98% or more. The average particle diameter of the obtained graft polymer was 0.18 μm.

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.

(C) Vinyl The formulation shown in Table 3 was kneaded for 5 minutes using a 6-inch test roll adjusted to 190°C to obtain a vinyl chloride resin composition. This assembly was pressed at a pressing temperature of 190°C and a pressing pressure of 1
The physical properties of the composite materials were measured by molding them into a press sheet with a thickness of 3 IllI at a pressure of 50 kg/cm''.The results are shown in Table 4. The results of measurements made in the same manner in place of the modifier and the results of measurements without the use of the modifier are also shown.

The physical properties of the Kumikaimono were measured by the following method.

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

・Weather resistance: 40 according to Sunshine Weatherometer
Conducted 0-hour and 1,000-hour accelerated exposure tests,
Thereafter, the above-mentioned notched Izod impact strength was measured at 23°C.

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

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

- Bending whitening property: 0. A 5 mm press sheet was prepared, the press sheet was bent, and the degree of whitening at the bent portion was observed.

Table 3 Modifier (graft polymer) 10 parts Polyvinyl chloride resin (1,050) 100 Dibutyltin Murray 2.5 "Calcol 86 0.8" Wasox OP 0.2" Comparative Example l Implementation A crosslinked rubber backbone polymer was prepared by operating in the same manner as in Example 1 (A), but using the same amount of allyl methacrylate instead of vinyltris(2-methoxyethoxy)silane as a crosslinking agent, and the following (B) A test piece of the vinyl chloride resin was prepared in the same manner as (C) and its physical properties were measured.

The results are shown in Table 4. Incidentally, during the production of the crosslinked rubber backbone polymer (A) and the graft polymer (B), the polymerization rate was 97% or more in both cases, and the polymerization was substantially completed.

Example 2 and Comparative Example 2 Crosslinked rubber backbone polymers were produced in the same manner as in (A) of Example 1 and Comparative Example 1, and the procedures shown in Table 5 were carried out in the production of the graft polymer of (B). Test pieces of vinyl chloride resin composites were prepared in exactly the same manner as in Example 1 and Comparative Example 1, except that the crosslinking agent shown was used, and the physical properties were measured. The results are shown in Table 5.

Incidentally, during the production of the graft polymer (B), the polymerization rate was 97% or more in all cases, and the polymerization was substantially completed. / / Example 3 and Comparative Example 3 (A) of Example 1 and Comparative Example 1. Operate in the same manner as (B), but the type and amount of crosslinking agent and the type of monomer,
Graft polymers were prepared using different amounts as shown in Table 6, and test pieces of vinyl chloride resin compositions were prepared in the same manner as in (C) below to measure their physical properties. The results are shown in Table 6. Incidentally, the polymerization rate during production of the crosslinked rubber backbone polymer (A) and the graft polymer (B) was 97% or more in all cases, and the polymerization was substantially completed. / //' / / / [Effect of the invention] As is clear from the above examples and comparative examples, the graft polymer using the specific organosilicon compound of the present invention as an essential crosslinking agent is used as a modifier. Although the resulting vinyl chloride resin composition is slightly inferior in transparency to that obtained when commercially available MBS resin is used as a modifier, it has impact resistance that is equal to or better than that when commercially available MBS resin is used as a modifier, and it also has much better weather resistance. ing. (4th
Table) Furthermore, compared to the case where the specific organosilicon compound of the present invention is not used as an essential crosslinking agent, the impact resistance, weather resistance, and processability are equivalent or higher, and the transparency is improved. Therefore, the resin can be used for outdoor applications such as agricultural materials, industrial parts, and construction materials, such as PVC window frames, sizing materials, industrial rigid boards, pipes, and corrugated boards with improved transparency. Can be done. Procedural amendment stamp button 1. Case description: Patent Application No. 242729 of 2007 2. Name of the invention Modifier and vinyl chloride resin composition 3. Relationship with the case of the person making the amendment Patent applicant: 3-35-58 Sakashita, Itabashi-ku, Tokyo 174 (288
) Kawamura, Representative of Dainippon Ink & Chemicals Co., Ltd.
Kuni Shigeru 4. Agent Address: Dainippon Ink & Chemicals Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103

Claims (1)

[Claims] 1. (A) Graft polymerization of a vinyl monomer in the presence of an aqueous dispersion of an acrylic crosslinked rubber backbone polymer using a vinyl group-containing silicon compound as a crosslinking agent. A modifier for vinyl chloride resins made of a vinyl graft polymer obtained by 2. The vinyl group-containing silicon compound as a crosslinking agent 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_lH_2_l-O-R_3 (where l is an integer of 1 to 3, R_3 is an alkyl group having 1 to 4 carbon atoms), X is ▲ mathematical formula, chemical formula, table etc. ▼ (However, m is 1 to 3
n represents an integer of 0 or 1]. The modifier according to claim 1. 3. The modifier according to claim 1, wherein the amount of the vinyl group-containing silicon compound used as a crosslinking agent is 0.1 to 10% by weight of the acrylic crosslinked rubber backbone polymer. 4. A vinyl chloride resin composition containing the modifier according to claims 1 to 3.