JPH0362840A - Vinyl chloride resin for laminated glass - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a vinyl chloride resin having excellent adhesive strength, and more particularly to a polyvinyl chloride resin for use in laminated glass that provides laminated glass with excellent penetration resistance and impact resistance. Regarding vinyl chloride resin.

(Prior Art) It has been known to use a plasticized polyvinyl butyral film as an interlayer film for safety laminated glass. However, this plasticized polyvinyl butyral film has a strong adhesion on the film surface, so there is a problem that the films adhere to each other during winding after film formation.In order to prevent such adhesion, the surface is embossed and further An anti-blocking agent such as bicarbonate of soda is sprayed.

On the other hand, it is known that a vinyl chloride-glycidyl methacrylate copolymer film containing about 40% by weight of a plasticizer is used as such a film with little self-reflection. or,
The use of an interlayer film made by adding a plasticizer to a copolymer obtained by copolymerizing at least one monomer selected from esters and vinyl ethers is proposed in Japanese Patent Publication No. 55-162451. The adhesion strength to glass can be improved by changing the glycidyl methacrylate content of these vinyl chloride copolymers, but increasing the glycidyl methacrylate content reduces the penetration resistance strength of the laminated glass. It is difficult to achieve both adhesive strength and penetration resistance.

In addition, the yield during polymerization may decrease, thermal stability may be insufficient,
It can also cause discoloration.

(Problems to be Solved by the Invention) An object of the present invention is to provide a vinyl chloride resin for laminated glass that has excellent adhesive strength and penetration resistance.

Thus, according to the present invention, (1) particles having a particle size of 5μ or less and having a higher epoxy group content in the outer shell than the epoxy group content in the core of the particle, and aggregates thereof; A vinyl chloride resin for laminated glass, (2) consisting of a copolymer of vinyl chloride, a monomer having an epoxy group, and an optional monomer copolymerizable with these (1) Provided is a vinyl chloride resin for laminated glass as described in .

(Means for Solving the Problems) Examples of the monomer having an epoxy group used in the present invention include glycidyl ethers of unsaturated alcohols such as allyl glycidyl ether and methallyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, Glycidyl p-vinylbenzony 1-, methylglycidyl itaconate, glycidyl ethyl maleate,
Examples include glycidyl esters of unsaturated acids such as glycidyl vinyl sulfonate and glycidyl(mec)allylsulfone-1, and epoxide olefins such as butadiene monooxide, vinylcyclohexene monooxide, and 2-methyl-56-nipoxyhexene.

Examples of monomers that can be copolymerized with these optional components include fatty acid vinyls such as vinyl acetate and vinyl propionate, olefins such as ethylene and propylene, and halogenated monomers such as vinylidene chloride and vinylidene fluoride. Examples include vinylidenes, vinyl ethers such as isobutyl vinyl ether, methyl vinyl ether, and cetyl vinyl ether, and allyl compounds such as allyl chloride and methyl allyl ether.

In order to obtain an epoxy group-containing vinyl chloride resin using these monomers, bulk polymerization, suspension polymerization, micro suspension polymerization,
Well-known methods for polymerizing vinyl chloride, such as emulsion polymerization, can be employed.

For example, when obtaining a glass interlayer film by a film forming process such as a calender roll method, an extrusion sheet casting method, or an inflation method, suspension polymerization is preferred.

When used as a plastisol, emulsion polymerization or microsuspension polymerization, which is used as a polymerization method for vinyl chloride resin for paste processing, is preferred for the purpose of maintaining appropriate fluidity of the plastisol. Although the effects of the present invention are manifested in any polymerization method, the effects are most pronounced in emulsion polymerization and microsuspension polymerization in which the particle size is small, such as 5 μm or less. If the particle size is larger than 5 μm, the epoxy groups will not necessarily be distributed in the outer layer of the particles, resulting in insufficient adhesion to glass.

In order to obtain the resin of the present invention using these polymerization methods, the monomer having an epoxy group is charged into the reaction system in the latter half of the polymerization reaction, or the charging rate is gradually increased during the polymerization reaction. In this way, the content of epoxy groups in the polymer forming the outer shell of the polymer is increased. As is well known, a vinyl chloride polymer does not dissolve in a monomer (vinyl chloride), and the polymer generated by the polymerization reaction precipitates in the monomer liquid. Therefore, if a monomer having an epoxy group is introduced in the latter half of the polymerization reaction, polymer particles and aggregates thereof having an outer shell made of a polymer containing a large amount of epoxy groups will undergo suspension polymerization or bulk polymerization. So you can get it. This structure is particularly noticeable in microsuspension polymerization in which the monomer liquid WJ diameter is around 1 μm. In addition, in emulsion polymerization, the site of the polymerization reaction during polymerization is the polymer surface that is always in contact with water, so the resin of the present invention can be obtained by adding a monomer having an epoxy group in the latter half of the polymerization reaction. .

The epoxy group content of the outer shell of the resin of the present invention is 0.1 to
If the weight is less than 0.1% by weight, the adhesive strength to glass will be insufficient, and if it is more than 5% by weight, it will be difficult to balance the penetration resistance.

Excessive heat is required for gelation and gelation, resulting in increased manufacturing costs.

The vinyl chloride resin of the present invention may be mixed with plasticizers, stabilizers, ultraviolet absorbers, antioxidants, lubricants, fillers, colorants, etc., depending on the purpose. Furthermore, it is also possible to mix resins that are compatible with vinyl chloride, such as other vinyl chloride resins, acrylic resins, and epoxy resins.

A wide variety of plasticizers that are generally called plasticizers for polyvinyl chloride can be used.

For example, aliphatic plasticizers include dioctyl adipate, butyl diglycol adivate, dioctyl azelate, dibutyl sebacate, diisodecyl adipate, etc., and phthalic acid plasticizers include dioctyl phthalate, dibutyl phthalate 1-, and Delphthalate, butylhenzyl phthalate, dilauryl phthalate,
Examples of phosphoric acid plasticizers include dioctyl phthalate, and examples of phosphoric acid plasticizers include tricylenyl phosphate, tricresyl phosphate, talesyl diphenyl phosphate-1.
Examples include ethyl phosphite and tributyl phosphate. Examples of epoxy derivatives include epoxidized soybean oil and epoxy fatty acid monoester.

Polyester plasticizers can also be used in some cases. The appropriate amount of plasticizer to be added is 20 to 80 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

If there is too much plasticizer, the film strength will decrease, and if it is too little, it will become hard.

Suitable heat stabilizers include alkylated tin compounds of fatty acids such as butyltin laurate, butyltin maleate, and octyltin maleate, and alkyltin-containing sulfur compounds such as di-normal octyltin bis(isooctylthioglycolic acid ester) salt. used for. It is also possible to use a metal soap type stabilizer together with these.

As ultraviolet absorbers, hensitriazoles are excellent, such as 2(2'-hydroxy-5'methylphenyl)benstriazole, 2(2'hydroxy-3'-tert-butyl-5'methylphenyl)-5-chloro Benzotriazole, 2(2'-hydroxy-3',
5'-tert-butylphenyl)-5-chloro-
Penztriazole, 2(2'-hydroxyl 4'-octoxyphenyl)benzo I-riazole and the like are preferably used.

Phenolic antioxidants are excellent as antioxidants, such as 2,6-ditertiary-butyl p-cresol, 2,2'-methylenebis(4methyl-6-tertiary-butylphenol), and 4,4'-butylidenebis. (
3-methyl-6-tert-butylphenol), 4
, 4'-thiobis(3-methyl-6-tertiarybutylphenol), and the like.

Furthermore, if necessary, a crosslinking agent, a thickener, a diluent, a silane type or ditanate type coupling agent, etc. are blended.

In order to manufacture laminated glass using the vinyl chloride resin of the present invention, there is a conventional method of forming a film and then sandwiching it between glasses and heating under pressure. On the other hand, as a new manufacturing method with higher productivity, published patent publication No. 63-134539
There is a method. In the case of this method, a well-known method for paste processing is used, such as a method in which compounding agents such as plasticizers, stabilizers, ultraviolet absorbers, and antioxidants are added to the vinyl chloride resin of the present invention, mixed, and defoamed. Prepare plastisol. Since plastisol can be handled as a liquid, dust and foreign matter can be removed by simply passing it through a filter, and storage and transportation can be done in a closed system such as a tank or pipeline, making quality control easy and suitable for automated continuous use. ing. Such plastisol is filled between glass plates, and the plastisol layer is gelled using a heating device used in normal paste processing, and then laminated with glass. Here, since it is the outer shell of the particle that comes into contact with the glass, high adhesive strength can be achieved if there are many epoxy groups serving as an adhesive component in the outer shell. Furthermore, since air bubbles are prevented from entering the plastisol during filling, a pressurizing device such as an autoclave is not required.

0 (Effects of the Invention) Thus, according to the present invention, it is possible to obtain a vinyl chloride resin for laminated glass that has superior adhesive strength and penetration resistance compared to conventional techniques.

(Example) The present invention will be described in more detail with reference to Examples below. Note that parts and percentages in Examples and Comparative Examples are based on weight unless otherwise specified.

Example 1 In a 10012 stainless steel autoclave, 160 parts of deionized water and 0 parts of dioctyl sulfosuccinate sodium were added.
．． After adding 4 parts of lauryl alcohol, 1 part of lauryl alcohol, and 0.4 parts of lauroyl peroxide and degassing under reduced pressure, vinyl chloride 97.
1 part to obtain an emulsion under stirring. This mixture was homogenized with a homogenizer and separated with another degassed 100
0 I! The mixture was then transferred to an autoclave and heated to 45°C to initiate polymerization. Five hours after the temperature was raised, the polymerization rate was 61%, so from this point on, glycidyl methacrylate-1
Three parts were continuously injected into autoclave 1 during polymerization over a period of 3 hours, and the polymerization was terminated after 10 hours. After recovering unreacted monomers under reduced pressure, the reaction solution was dried using a spray dryer and pulverized to obtain a resin.

To 100 parts of this resin, 45 parts of dioctyl adipate, 15 parts of dioctyl phthalate, 4 parts of dibutyltin polymercaptide, 2,2'-methylenebis(4-methyl-6-
0.3 part of tertiary-butylphenol was mixed in a Hobart mixer and defoamed under reduced pressure to obtain plastisol. This plastisol is 15c+nX 10cm, thickness 3mm
A 20 μm thick polyethylene terephthalate film was applied on a glass plate using a doctor blade, and then a 0.8 mm thick resin layer was heated at 200°C for 15 minutes to prevent air bubbles from appearing. Obtained bi-layer glass. Also, this plastisol is 30cm x 30cm.

The coating was applied to a 3n+m thick glass plate using a roll coater, and then a 30cm x 30cm, 3cm thick glass plate was gently placed on top of it, taking care not to introduce air bubbles, and heated at 200°C for 15 minutes. Two sheets of 8 mm laminated glass were obtained.

2 Example 2 160 parts of deionized water, 0.4 parts of sodium dioctyl sulfosuccinate, 1 part of lauryl alcohol, and 0.4 parts of lauroyl peroxide were placed in a 1000 ffi stainless steel autoclave, and after degassing under reduced pressure, 94% of vinyl chloride was prepared. 1 part and 3 parts of allyl chloride were charged to obtain an emulsion with stirring. The mixture was homogenized with a homogenizer and transferred into another degassed 1000j2 autoclave,
Polymerization was initiated by raising the temperature to 52°C. Below, 45 parts of dioctyl adipate of Example 1, 1 part of dioctyl phthalate
The procedure was repeated in the same manner as in Example 1, except that 5 parts were changed to 130 parts of dioxyl adiper and 10 parts of sucoctyl phthalate, to obtain a pie layer glass (2) and two sheets of laminated glass (2).

Example 3 160 parts of deionized water, 0.4 parts of sodium dioctyl sulfosuccinate, 1 part of lauryl alcohol, and 0.4 parts of lauroyl peroxide were placed in a 1000 ffi stainless steel autoclave, and after degassing under reduced pressure, 96% of vinyl chloride was dissolved. 5 parts were charged, and a third emulsion was obtained under stirring. The mixture was homogenized using a homogenizer, transferred to another degassed 1000 ffi autoclave, and heated to 45°C to initiate polymerization.

1.5 parts of glycidyl methacrylate was injected from the start of polymerization to 6 hours, 12 parts of glycidyl methacrylate was injected from 6 to 8 hours, and the polymerization was terminated 10 hours later. Thereafter, operations were carried out in the same manner as in Example 1 to obtain pie layer glass (2) and two pieces of laminated glass (2).

Example 4 A hydroperoxide emulsion was prepared by mixing log of cumene hydroperoxide, 10 g of t-butyl hydroperoxide, 500 g of sodium lauryl sulfate, and 10 kg of deionized water using a high-speed stirrer. Further, an emulsifier aqueous solution was prepared by mixing 1.6 kg of sodium lauryl sulfate and 28.5 kg of deionized water.

Now, in a 10001 stainless steel autoclave, 325 kg of deionized water, 50 kg of latex containing 30 weight percent of vinyl chloride homopolymer resin particles with an average particle size of 0.45 μm, and 150 g of R-ascorbic acid.
, 6 g of ferrous ion sodium ethylenediaminetetraacetic acid salt, and 2.5 kg of sodium pyrophosphate were charged, and nitrogen substitution and vacuum degassing were performed twice each. Then vinyl chloride 35
Charge 7.5 kg and heat the contents from the jacket of the autoclave while stirring to bring the temperature of the contents to 50°.
After reaching C, the emulsifier aqueous solution and the hydroperoxide emulsion were added to the reaction system with δ of 2.81 each.
! /hr, 11! The reaction temperature was maintained at 50°C while introducing at a rate of /hr. The emulsifier aqueous solution is 1 at the same rate.
The hydroperoxide emulsion was introduced for 0.5 hours and then stopped, but after 6 hours, the reaction conversion rate of the hydroperoxide emulsion was 40.
At the 5% point, the rate was switched to 0.71/hr and 15.9 kg of glycidyl methacrylate was injected at a rate of 3 kg/hr. In this manner, the reaction was completed after a total reaction time of 12 hours and 10 minutes, and the mixture was cooled. The reaction conversion rate was 91.
It was 3%. With cooling, sodium lauryl sulfate 0,
5 kg and polyoxyethylene sorbitan monostearate 1. After dissolving Okg in 10 kg of deionized water and injecting the solution into the 5 system, unreacted monomer was recovered.

Thereafter, operations were carried out in the same manner as in Example 1 to obtain two pieces of high layer glass (■) and two sheets of laminated glass (■).

Comparative Example 1 The same procedure as in Example 1 was carried out except that glycidyl methacrylate was injected 5 hours after the temperature was raised in Example 1, but was continuously injected for 8 hours immediately after the temperature was raised, and combined with the bilayer glass ■. Two pieces of glass were obtained.

Comparative Example 2 Commercially available interlayer film for laminated glass (made of polyvinyl butyral,
30n+il) was adjusted to have a moisture content of 0.5wt%, and placed on a 30cm x 30cm, 3mm thick glass plate was the above humidity controlled interlayer film, a 20μm thick polyethylene terephthalate film, 30cm x 30cm, thickness 31 cover glasses were laminated in this order (laminate I). Put this laminate 1 into a rubber bag, reduce the pressure inside the bag,
Preliminary pressure bonding was performed by holding at 120°C for 30 minutes. Similarly, a glass plate 2 of 30cm x 30cm and 3mm thick
The above humidity-controlled interlayer film 6 was sandwiched between the sheets, and 4-factor preliminary pressure bonding was performed using a rubber bag to obtain a laminate of 2.2 mm. Next, laminate 1
, 2 in a pneumatic autoclave at 140°C 1 ■ 3 ~ 1
Pressure and heat compression bonding was carried out for 30 minutes at a pressure of 5 kg/cm''.Finally, the cover glass of the laminate J was removed to obtain two laminated glass plates made of pie layer glass.

In order to investigate the performance of the laminated glass obtained in Examples 1 to 3 and Comparative Examples 1 to 2, transparency and
The penetration resistance, impact resistance, and adhesive strength were measured, and the results are shown in the table.

1. Transparency (visible light transmittance) Laminated glass ■～■ was measured with a spectrophotometer (manufactured by Hitachi, Ltd.) at 38
Transmittance was measured from 0 nm to 750 nm.

2. After leaving the laminated glass ■~■ whose penetration resistance strength and transparency were measured in an atmosphere of 20'C for 2 hours, a 2.27k mark was placed in the center of this laminated glass.
Drop a steel ball g from a height of 4 m and check whether there is any penetration 7.

3. Impact resistance - Laminated glass sheets ■～■ under an atmosphere of 23°C.
After standing for a period of time, a 227 g steel ball was dropped from a height of 9 m, and the total weight of the smoldered glass was measured from the opposite side of the impact surface.

4. Adhesive strength After leaving the Pylayer glass ■～■ in an atmosphere at 23°C for 2 hours, part of the interlayer film was peeled off and bonded at 300mm/mi.
Measure the T-peel adhesive strength at a speed of n.

The evaluation results are shown in the table. From the table, the laminated glass according to the present invention can satisfy the performance of laminated glass.

8 ■ 9

[Brief explanation of drawings]

FIGS. 1 and 2 are cross-sectional photographs of particles taken using an electron microscope, and the structure of the particles can be understood from these photographs. That is, the first
The figure shows a cross section of the particles obtained in Example 1, in which the outer layer of the particles containing epoxy groups is dyed darker than the ruthenic acid. On the other hand, FIG. 2 shows the particles obtained in Comparative Example 1 subjected to the same treatment, and it can be seen that the entire particles have approximately the same brightness and the epoxy groups are distributed almost uniformly throughout the particles.

Claims (2)

[Claims] (1) A vinyl chloride resin for laminated glass consisting of particles and aggregates thereof, which have a particle size of 5 μm or less and have a higher epoxy group content in the outer shell than in the core of the particles. (2) The laminated glass according to claim 1, which is made of a copolymer of vinyl chloride, a monomer having an epoxy group, and an optional monomer copolymerizable with these. vinyl chloride resin