JPH03244648A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in adhesiveness and good in gelation rate, moldability, dynamic heat resistance, and impact strength by compounding a vinyl chloride resin with a copolymer of a metal carboxylate group-contg. vinyl ester with ethylene. CONSTITUTION:The title compsn. is obtd. by compounding a vinyl chloride resin with a copolymer of a metal carboxylate group-contg. vinyl ester with ethylene. As the copolymer, the one obtd. by copolymerizing a metal carboxylate group-contg. vinyl monomer is pref., and the one obtd. by introducing a metal carboxylate group under the condition of grafting is esp. pref. because of its excellent effects. The compsn. is useful in a wise application area, such as for producing a rigid film and sheet by calendering and for extruding a profile- extruded building material, pipe, etc., esp. suitable for producing a sheet which is laminated to a plywood using an adhesive to make a building material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a vinyl chloride resin (hereinafter abbreviated as PVC) composition suitable for sheets, molded products, etc.

[Conventional technology]

Various polymer processing aids are used for the purpose of improving the moldability of PvC. A typical example is a polymer whose main component is polymethyl methacrylate. However, although this polymer is excellent in increasing the gelation rate, it has a high melt viscosity and poor fluidity. In addition, the heat generated during kneading is large and the time until PVC thermal decomposition is shortened, resulting in poor dynamic heat resistance. Furthermore, in terms of physical properties, there was a drawback in that although the thermal softening temperature did not decrease, the impact strength decreased. On the other hand, vinyl ester-ethylene copolymer (hereinafter abbreviated as VEE) is also used as a processing aid for PVC. Since VER has rubber-like properties, it does not reduce impact resistance, it actually reduces melt viscosity, and it does not deteriorate dynamic heat resistance. Therefore, it is preferably used in applications where the generation of air bubbles (air marks) in the sheet and dynamic heat resistance are problematic, such as in hard calendar applications. However, it is inferior to the above-mentioned polymethyl methacrylate in terms of increasing the gelation rate.

Furthermore, an IJ1 material has been proposed in which a VER having a carboxyl group or an epoxy group is added to PVC to increase the gelation rate and have excellent dynamic heat resistance, processing safety, and impact resistance.

However, VEE having a carboxyl group or an epoxy group
PvC compositions to which PvC is added have a disadvantage in that their adhesion to plywood decreases when used as a sheet for building materials that adheres to plywood.

[Problem to be solved by the invention]

An object of the present invention is to provide a PVC [acid] which has excellent adhesive properties, particularly adhesive properties to plywood, and which has practically satisfactory gelation rate, moldability, dynamic heat resistance, and impact strength.

[Means to solve the problem]

The present inventors investigated the m-parabolites of various PVCs, and as a result, arrived at the present invention by blending VEE having a carboxylic acid metal base into PvC.

That is, the present invention provides a PvC composition characterized in that a carboxylic acid metal base-containing VEE is blended with 100 parts by weight of PVC.

In the present invention, the VEE to be used with a carboxylic acid metal base introduced therein is preferably one having a vinyl ester content of 25 to 75% by weight, and in particular, one having a vinyl ester content of 45 to 65% by weight has particularly good transparency and gels. PVC&I is more preferable because it has a fast conversion rate and excellent impact strength.

VP and E used here are obtained by copolymerization of vinyl ester and ethylene, and the polymerization method may be any one of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization. Examples of the vinyl ester include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate, each of which may be used alone or in combination of two or more, with vinyl acetate being particularly preferred.

The carboxylic acid metal base-containing VER used in the present invention is preferably one obtained by copolymerizing a carboxylic acid metal base-containing vinyl monomer, and among them, one in which a carboxylic acid metal base is introduced under graft polymerization conditions is effective. It is preferable because it has excellent properties.

The carboxylic acid metal base-containing vinyl monomers include Mg5Af of carboxyl group-containing vinyl monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and cinnamic acid.
, Ca, Zn, Ba, Pb, and other metal salts.

In addition, when introducing the carboxylic acid metal base, if necessary, vinyl monomers other than the above-mentioned vinyl monomers, such as fatty acid vinyl esters such as vinyl acetate and vinyl propionate, ethyl acrylate, methyl acrylate, hydroxyethyl acrylate, hydroxy VE alkyl esters of acrylic acid or methacrylic acid such as propyl methacrylate and methyl methacrylate, aromatic vinyls such as styrene, vinyl cyanides such as acrylonitrile, etc.
E may be used in combination in an amount of 50 parts by weight or less per 100 parts by weight.

General polymerization methods such as melt grafting using an extruder or graft polymerization in a solution can be used to introduce the carboxylic acid metal base-containing vinyl monomer into VEE. It is done as follows. That is, a carboxylic acid metal base-containing vinyl monomer is added to VEE in a suspended state, the monomer is absorbed into VEE particles, and then polymerization is carried out using a radical initiator at an elevated temperature. Examples of the agent include benzoyl peroxide, azobisisobutyronitrile, L-butyl peroxybenzoate, t-butyl peroxy (2-ethylhexanoate), diisopropyl peroxy carbonate, L-butyl peroxy pivalate, t- -butyl peroxyisopropyl carbonate, t-butyl lauryl peroxide, etc., and are usually added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the vinyl monomer for polymerization. The polymerization temperature varies depending on the radical initiator used, but is generally 60 to 130°C, and the produced modified 1iVEE in a suspended state is separated from water, washed, and dried. At that time, anti-blocking agents such as wax, silicone oil, silica, calcium carbonate, magnesium oxide, calcium stearate, etc. may be used, and the amount added is usually 0.1 to 10 parts by weight per 100 parts by weight of modified VEE. Department.

PvC used in the present invention refers to vinyl chloride homopolymers and monomers copolymerizable with vinyl chloride, such as vinyl esters such as vinyl acetate; olefins such as ethylene; acrylic acid, methacrylic acid, and their alkyl esters; Copolymers with vinyl chloride containing vinylidene in an amount of 30% by weight or less, ethylene-vinyl acetate copolymers, chlorinated polyethylene, graft copolymers with vinyl chloride added to thermoplastic polyurethane, etc. can also be used.

The carboxylic acid metal base content VER is preferably 0.5 to 20 with respect to 100 parts by weight of the PVC composite bottom acid VC of the present invention.
Parts by weight, more preferably 3 to 10 parts by weight, have improved properties, and in this case, such VEE
If the amount is less than 0.5 parts by weight, the effect of promoting gelation cannot be improved, and if it is more than 20 parts by weight, the heat softening temperature of the molded product will be lowered, which is not preferable.

The PVC&II of the present invention may contain oxidizing agents, pigments, ultraviolet absorbers, lubricants, plasticizers, impact modifiers, flame retardants, crosslinking agents, blowing agents, fillers, and other additives as necessary. can do.

The bottom shape of the PVCM samurai of the present invention is formed by conventional mixing roll processing, calendar processing, extrusion molding, injection molding, etc.

PVC of the present invention! The 11th precept has a short gelation time and a long thermal decomposition time at the processing temperature, so it has a wide range of stable processing time, and its physical properties include transparency, mechanical strength, and
Improved impact resistance while maintaining adhesion to plywood.

As mentioned above, the trade-offs in the properties of conventional processing aids have been resolved, making them useful not only in hard films and sheets made by calendar processing, but also in a wide range of fields such as irregularly extruded building materials and pipes made by extrusion processing. It is particularly effective for use in building material sheets that are bonded to plywood.

[Example] Next, in order to further clarify the characteristics of the present invention, the present invention will be specifically described using Examples. Note that all percentages other than parts and transparency in Reference Examples, Examples, and Comparative Examples are based on weight. The physical property evaluation methods used in the Examples and Comparative Examples are as follows.

1. Processing of PVC Composite Anatomy 1-1 Using Gellable Brahender Plast Graft (PLV-151), track the kneading torque curve of the PVC composition under the following conditions and determine the time to the first peak. It was measured as gelation time (GT), and if the gelation time was less than half that of one without the addition of a processing aid, it was considered to have passed.

Jacket temperature 190'C Rotor rotation speed 3Qrpm Sample filling amount
60g 1-2 Measured using the same method as the dynamic heat-resistant gelation property, and if the time to the second peak is taken as the decomposition time (DT) and it is 22 minutes or more under these measurement conditions, there is no practical problem and it is passed. And so.

1-3 Processing stability Furthermore, as a measure of processing stability, the gel ratio decomposition time was calculated using the following formula. The larger the time width is, the longer the allowable time for stable processing of the compound is.If this time is 22 minutes or more, it is considered to be acceptable without any practical 1' or T problems.

Gel specific table Decomposition time = DT-GT (min) 1-4 ff
Surface quality of the mold (air mark) The gap between the two rolls is set to 0.
3III11, and 100 parts by weight of the PVC composition was immersed at 190° C. for 5 minutes, and then the rolled sheet was observed and the state of air bubble entrainment was evaluated. If the entrainment of air bubbles is the same or less than that of a formulation without the addition of a processing aid, there is no practical problem, so it was passed.

2. Physical properties: Two PVC 11 precepts (D o-runite at 190°C
After kneading for a minute, specimens suitable for the following evaluation physical properties were prepared using a press machine, and each physical property was measured.

2-1 Transparency The light transmittance of a press sheet with a lum thickness was measured.

If the light transmittance was 85% or more, there would be no practical problem, so it was judged as a pass.

2-2 Heat softening property: Performed according to JIS K-6745, softening temperature is 60°
If it is C or higher, there is no practical problem, so it was passed.

2-3 Impact resistance It was conducted according to JIS K-6745, and if the Charpy impact value was 18 kg-cm/cm" or more, there was no practical problem and the test was passed.

2-4 Adhesion A rolled sheet of 0.3gl111 thickness was adhered to plywood using a vinyl acetate emulsion adhesive, and when a certain area of the sheet was peeled off at O''C, wood chips were found on the sheet.

The ratio of the area is expressed as the percentage of wood damage (%), and if it is 95% or more, there is no problem in practical use, so it was passed.

Reference Example 1 160 parts of vinyl acetate, 800 parts of distilled water, 1.6 parts of azobisisobutyronitrile (polymerization catalyst), 1.6 parts of polyvinyl alcohol (dispersant), and Sodium acrylate (dispersant) 0
．． After charging 8 parts of the autoclave, the air in the autoclave was replaced with nitrogen, and ethylene was injected at 30°C to a rate of 68 kg/cm.The internal temperature was then raised to 65°C and suspension polymerization was carried out for 9 hours. Ta.

When the residual ethylene was released and the temperature was returned to room temperature and normal pressure, a suspension of vinyl acetate-ethylene copolymer (1) (hereinafter abbreviated as V A E (1)) with a vinyl acetate content of 491% was formed. Ta. 0.7 parts of polyvinyl alcohol (dispersant), 76 parts of methyl methacrylate, 4 parts of zinc acrylate, and 1.6 parts of benzoyl peroxide (polymerization catalyst) were added to this V A E (1) suspension, and the mixture was heated to room temperature. Stirring was continued for 2 hours at a temperature to allow the vinyl monomer and initiator to be absorbed into the suspended particles. Thereafter, the temperature was raised to 75°C and polymerization was carried out for 5 hours. After washing the obtained particles, they were dried at 50''C for 24 hours to obtain 395 parts of modified V A E (A).

Reference Example 2 Modified VAE (
B) 39El was obtained.

Reference Example 3 13 parts of zinc acrylate was used instead of 76 parts of methyl methacrylate and 4 parts of zinc acrylate, and 0.0 parts of benzoyl peroxide was used instead of 1.6 parts of benzoyl peroxide.
Modified VAE (
C) 330 parts were obtained.

Reference Example 4 Modified 1iVAE (D
) 353 copies were obtained.

Reference Example 5 392 parts of modified V A E (E) was obtained in the same manner as in Reference Example 1 except that 80 parts of methyl methacrylate was used instead of 76 parts of methyl methacrylate and 4 parts of zinc acrylate.

Reference Example 6 476 parts of modified V A E (F) was obtained in the same manner as in Reference Example 1 except that 160 parts of methyl methacrylate was used instead of 76 parts of methyl methacrylate and 4 parts of zinc acrylate.

Reference Example 7 A 63% VAE containing vinyl acetate was prepared in the same manner as in Example 1 except that the ethylene saturation pressure was changed to 55 kg/cm.
(2) 248 parts were obtained.

Reference Example 8 Modified 1tVAE (G
) 384 copies were obtained.

Reference Example 9 Modified V A E (H) was prepared in the same manner as Reference Example 1 except that 60 parts of methyl methacrylate and 20 parts of glycidyl methacrylate were used instead of 76 parts of methyl methacrylate and 4 parts of zinc acrylate. I got the department.

Example 1 100 parts of PVC with a degree of polymerization of 800, 6 parts of MBS resin (Kane Ace B-12 manufactured by Kanebuchi Kagaku Co., Ltd.), 1.5 parts of octyltin mercapto, 1 part of glycerin monostearate, and modified [V
8 parts of AE (A) was applied to a Brabender plastograft to evaluate gelling properties, dynamic heat resistance, and processing stability. Separately, a PVC composition of the same composition was kneaded using two kneading rolls, and the surface properties, transparency, softening temperature, impact resistance, and adhesion to plywood of the molded products were evaluated.

The results are shown in Table-1.

Examples 2-3 Modified VAE (A) (7) Instead of modified VAE (B
) or (C) was used, but the evaluations were carried out in the same manner as in Example 1, and the results shown in Table 1 were obtained.

Comparative Examples 1 to 5 Modified VAE (A) + 7) Instead of modified VAE (D
), (E), (F), VAE (1) or VAE
Various evaluations were performed in the same manner as in Example 1 except that (2) was used, and the results shown in Table 1 were obtained.

Comparative Example 6 Each evaluation was performed in the same manner as in Example 1 except that the addition of modified VAE (A) was omitted, and the results shown in Table 1 were obtained.

Comparative Example 7 Modified V A E (A) was replaced with a commercially available methacrylate processing aid (ethyl acrylate/methyl methacrylate)
Example 1 except that -10 parts/90 parts copolymer) was used.
Each evaluation was performed in the same manner as above, and the results shown in Table 1 were obtained.

Comparative Examples 8-9 Each evaluation was performed in the same manner as in Example 1, except that modified VAE (A) f7) was replaced with modified ■AE (G) or (H), and the results shown in Table 1 were obtained. Ta.

〔Effect of the invention〕

The present invention provides a PVC composite oxide which has excellent adhesive properties, particularly adhesive properties to plywood, and which is practically effective in terms of gelling speed, moldability, dynamic heat resistance, and impact strength.

teenager Reason Man

Claims (1)

[Claims] A vinyl chloride resin composition comprising a vinyl chloride resin and a vinyl ester-ethylene copolymer containing a carboxylic acid metal base.