JPS5856536B2 - Vinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a vinyl chloride resin composition having good processability, particularly good peelability from high-temperature metal surfaces, specifically alkyl acrylate, copolymerizable vinyl chloride resin composition, etc. The present invention relates to a novel vinyl chloride resin composition comprising a copolymer of a mixture of acrylate and/or methacrylate having an oxygen atom in addition to an ester bond, and a vinyl chloride resin or a vinyl chloride resin mixture.

Although vinyl chloride polymers are excellent in physical properties, economical efficiency, and usability, they have the drawback of poor processability in various ways.

That is, it has a high melt viscosity, poor fluidity, and is easily thermally decomposed, which not only narrows the molding area but also tends to stick to the metal surface of equipment during high-temperature processing.

However, the utility of vinyl chloride-based polymers can be increased by physically mixing various modifiers prior to processing.

These modifiers include materials such as lubricants, stabilizers, colorants, fillers, pigments, crosslinkers, adhesives, plasticizers, processing aids, impact modifiers, and heat distortion temperature modifiers.

The present invention relates to vinyl chloride-based polymers containing a resin modifier that acts as a processing aid. Substantial improvements are made during extrusion, rolling, and rolling.

Particularly when the modifier of the present invention is added to polyvinyl chloride,
Provides excellent roll release at high temperatures and resistance to 'plate-out'.

Furthermore, in extrusion, long-time extrusion is possible.

In order to improve the moldability of vinyl chloride polymers,
Some copolymers that are compatible with vinyl chloride polymers have been studied as processing aids.

Namely, a method of adding a copolymer of methyl methacrylate and styrene (Japanese Patent Publication No. 32-4140), a method of adding a copolymer of styrene and acrylonide (Japanese Patent Publication No. 29-524)
6), method of adding a copolymer mainly composed of methyl methacrylate (Japanese Patent Publication No. 4 O-5311), method of adding a copolymer of styrene and alkyl acrylate (Japanese Patent Publication No. 37-1989)
18864).

All of these accelerate the gelation rate of vinyl chloride polymers and improve secondary processability such as increasing tensile elongation at high temperatures, but they do not have the effect of reducing adhesion to the metal surface of the molding machine. Totally unacceptable.

The present invention solves the above problems, and the CI, l
100 parts by weight of a vinyl chloride resin or a vinyl chloride resin mixture consisting of 100 to 50% by weight of a vinyl chloride resin and 50 to 0% by weight of another thermoplastic resin, and (I) 99.9 to 20% by weight of ester bonds. Alkyl acrylates having no other oxygen atoms, 79.9~O
% by weight of other copolymerizable vinyl monomers, 10-0.1
This is a vinyl chloride resin composition comprising 10 to 0.1 parts by weight of a copolymer of a mixture of acrylate and/or methacrylate having oxygen atoms in addition to ester bonds.

The present invention provides a vinyl chloride resin composition that has excellent long-term lubricity properties such as peelability from metal surfaces.

The present invention will be explained in detail below.

The vinyl chloride resin referred to as the acid component [■] in the present invention includes a homopolymer and/or copolymer in which at least 80% by weight is vinyl chloride, and post-chlorinated polyvinyl chloride.

This vinyl chloride copolymer may be copolymerized with 20% by weight or less of a monovinylidene compound such as vinyl acetate, methyl methacrylate, butyl acrylate.

In addition, the other thermoplastic resin in the [I] acid component is MBS
It includes all conventional thermoplastic resins that can be mixed with vinyl chloride resins such as resins, ABS resins, and As resins.

The amount of the copolymer component used in the present invention is 0.1 to 10 parts by weight, preferably 0.5 to 3.0 parts by weight.

If the amount is less than 0.1 part by weight, no effect can be achieved, and if it exceeds 10 parts by weight, the original characteristics of the vinyl chloride resin will be lost.

The above component (II) will be explained in detail. [of the present invention]
■] Acid component characteristic is that it is a copolymer obtained by polymerizing a mixture consisting mainly of alkyl acrylates that do not have oxygen atoms other than ester bonds, and small amounts of acrylates and/or methacrylates that have oxygen atoms other than ester bonds. It is in.

Blends of copolymers of alkyl acrylate and aromatic vinyl, copolymers of alkyl acrylate and methyl methacrylate, and polyvinyl chloride are known, but alkyl acrylate and a small amount of acrylate having an oxygen atom in addition to an ester bond and/or This is a new fact that has not been suggested at all that a copolymer made of methacrylate can dramatically improve the peelability of a vinyl chloride resin composition from a high-temperature metal surface.

The component of the present invention may contain a commonly used chain transfer agent such as tertiary dodecyl mercaptan, if necessary.

The preferred amount of chain transfer agent is 0.5-3% by weight, C
1l, ] The molecular weight of the component is approximately 10,000-300
,000 is preferable.

Examples of acrylates and methacrylates having an oxygen atom in addition to an ester bond include hydroxyacrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate, hydroxymethacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxyethyl methacrylate, and methoxyethyl acrylate. , alkoxy acrylates such as ethoxyethyl acrylate,
Examples include alkoxy methacrylates such as methoxyethyl methacrylate and ethoxyethyl acrylate, epoxy group-containing acrylates such as glycidyl acrylate, and epoxy group-containing methacrylates such as glycidyl methacrylate.

These can be used alone or in combination of two or more.

It is essential that these be contained in an amount of 0.1 to 10% by weight in order to exhibit an excellent peeling effect from a high-temperature metal surface, and below or above this range, no significant peeling effect can be expected.

For the purposes of the present invention, the most preferred amount of acrylate or methacrylate having an oxygen atom in addition to the ester bond is 0.2 to 3.0% by weight.

[1] Acid component of the present invention [1] As the alkyl acrylate having no oxygen atom other than the ester bond, those in which the alkyl group has 3 to 8 carbon atoms, such as 2-ethylhexyl acrylate, butyl acrylate, and ethyl acrylate, are preferable.

Examples of the Bicol monomer in the copolymer side component of the present invention include alkyl methacrylates such as methyl methacrylate, aromatic vinyls such as styrene and α-methylstyrene, and acrylonitrile, which are copolymerizable with alkyl acrylates. These may be used alone or in combination of two or more, and aromatic vinyls such as styrene and α-methylstyrene are preferably used.

The polymerization of component (4) of the present invention is easily carried out by a conventional emulsion polymerization method using a thermal decomposition type initiator such as KPS or a redox type initiator.

In addition, in the [■] acid component polymerization of the present invention, in order to freely adjust the powder properties after drying, methyl which gives a hard polymer with good compatibility with the vinyl chloride polymer in the presence of the [α]] component polymer. Those obtained by further adding and polymerizing ethylenically unsaturated monomers such as methacrylate, vinyl chloride, and styrene, and (4)) in the presence of polymethyl methacrylate or polyvinyl chloride during polymerization of the component polymer [■]
One of the embodiments of the present invention is one in which polymerization of extraneous components is performed.

[■]] A hard polymer latex having good compatibility with the polymer and the vinyl chloride polymer may be blended in a latex state.

The present invention will be explained in detail in Examples below.

Note that % and parts indicate weight % and parts by weight.

Example 1 In a reaction vessel equipped with a stirrer and a cooler, 200 parts of distilled water, 1.0 part of sodium dioctyl sulfosuccinate, 0.01 part of sodium ethylenediaminetetraacetate, and Fe
200,005 parts of SO4.7H and 1.0 part of sodium formaldehydrosulfite are charged.

Next, after purging the inside of the container with nitrogen, the reaction container was heated to 60°C while stirring.
The temperature was raised to 0°C, and 39 parts of butyl acrylate and 5 parts of styrene were added.
A mixture of 9 parts of 2-hydroxyethyl acrylate, 1-1.0 parts of 2-hydroxyethyl acrylate, and 1.0 parts of tertiary dodecyl mercapkune was added over 6 hours, and after the addition was complete, the mixture was further stirred for 2 hours to complete the polymerization. .

The obtained emulsion was cooled, salted out using calcium chloride, and dried to synthesize sample (4).

Example 2 Polymer (4) obtained in Example 1 and other polymers shown in Table 1 and produced by a similar method were blended with polyvinyl chloride according to the following method to improve peelability from the hot roll surface. I received an evaluation.

A mixture of 100 parts of polyvinyl chloride, 1 part of the sample shown in Table 1, 2 parts of a tin-based stabilizer, and 1.0 part of a lubricant was kneaded at 190°C using a 6-inch roll, and after 10 minutes there was no peeling from the roll surface. compared gender.

Evaluation is based on the usual 10-point system, with 10 being the best peeling property and 1 being the best peeling property.
is the minimum.

That is, the closer the value is to 10, the better the peelability is.

Example 3 The polymer obtained according to Example **1 except that 1.0 part of 2-hydroxyethyl acrylate was replaced with the monomer shown in Table 2 was blended with polyvinyl chloride, and the roll peelability was evaluated. .

Claims (1)

[Scope of Claims] 1 [I] 100 parts by weight of a vinyl chloride resin or a vinyl chloride resin mixture consisting of 100 to 50% by weight of a vinyl chloride resin and 50 to 0% by weight of another thermoplastic resin; (II) Other vinyl monomers that can be copolymerized with 99.9 to 20% by weight of alkyl acrylates having no oxygen atoms other than ester bonds, and 0.1 to 10% by weight of acrylates and/or methacrylates having oxygen atoms in addition to ester bonds. Copolymer consisting of 0 to 79.9% by weight 0.
A vinyl chloride resin composition comprising 1 to 10 parts by weight. 2. The vinyl chloride resin composition according to claim 1, wherein the acrylate having an oxygen atom in addition to the ester bond is a hydroxyacrylate. 3. The vinyl chloride resin composition according to claim 1, wherein the acrylate having an oxygen atom in addition to the ester bond is an alkoxy acrylate. 4. The vinyl chloride resin composition according to claim 1, wherein the acrylate having an oxygen atom in addition to the ester bond is an epoxy group-containing acrylate. 5. The vinyl chloride resin composition according to claim 1, wherein the methacrylate having an oxygen atom in addition to the ester bond is hydroxymethacrylate. 6. The vinyl chloride resin composition according to claim 1, wherein the methacrylate having an oxygen atom in addition to the ester bond is an alkoxy methacrylate. 7. The vinyl chloride resin composition according to claim 1, wherein the methacrylate having an oxygen atom in addition to the ester bond is an epoxy group-containing methacrylate.