WO2003011788A1

WO2003011788A1 - Resin composition for laminated glasses

Info

Publication number: WO2003011788A1
Application number: PCT/JP2002/007586
Authority: WO
Inventors: Norio Nagata; Mamoru Kadokura
Original assignee: Kaneka Corporation
Priority date: 2001-07-30
Filing date: 2002-07-26
Publication date: 2003-02-13
Also published as: JP2003040654A

Abstract

A resin composition for laminated glasses which is prepared by blending a plasticized polyvinyl acetal with a polymer having a multilayer structure to thereby overcome the disadvantages of intermediate sealing layers of laminated glasses of the prior art, specifically a resin composition for laminated glasses comprising 8 to 45 % by weight of a polymer having a multilayer structure and 55 to 92 % by weight of polyvinyl acetal, wherein the polymer is composed of 40 to 85 % by weight of an inner layer and 60 to 15 % by weight of an outer layer, the inner layer comprising an alkyl acrylate rubber and/or a conjugated diene rubber and the outer layer being a hard one produced by polymerizing an alkyl methacrylate and/or an alkyl acrylate.

Description

Akira Itoda

Resin composition for laminated glass

Technical field

The present invention relates to a resin composition for an interlayer film for laminated glass.

Background art

Conventionally, laminated glass has been widely used as window glass for automobiles and buildings. In this laminated glass, an interlayer film for laminated glass formed by forming a plasticized polypieracetal resin such as a polyvinyl butyral resin plasticized by a plasticizer is interposed between at least a pair of glasses to be integrated. Typical products are those made by Such laminated glass

It must have good transparency, weather resistance and adhesion, and also have excellent penetration resistance. That is, if an impact is applied to this, the glass is broken, but the interlayer film interposed between the glass is not easily broken, and the glass remains attached to the interlayer film even after the breakage. Fragments are rarely scattered. Therefore, for example, it has a function of preventing a human body inside a car or a building from being injured by broken glass.

For this intermediate film, a resin composition for a laminated glass using a resin composition comprising a polyvinyl acetal resin, a plasticizer and a metal salt is usually used in order to ensure adhesion and penetration resistance. However, when a metal salt is contained as in this resin composition, the moisture absorption rate of the composition increases, and the resin in the periphery of the laminated glass is in contact with the atmosphere, and a whitening phenomenon is observed. This is a major problem. Therefore, if a strength improver that can improve the strength of polyvier acetal besides adding a plasticizer and a metal salt can be developed, it would be an obstacle. The amount of components that cause the above-mentioned harmful phenomena can be reduced, and a blend that is advantageous in practical use can be obtained.

The present invention relates to the development of a strength improver other than a plasticizer and a metal component for improving the strength of polyviel acetate in order to solve the above-mentioned problems. Specifically, the present invention relates to a laminated glass resin composition having improved penetration resistance by imparting impact strength and elongation at break to the resin composition while maintaining good adhesion of the resin composition to glass. Offer things. Disclosure of the invention

The resin composition for a laminated glass according to the present invention improves the disadvantages of the laminated glass interlayer by blending a multi-layered polymer with a plasticized polyvinyl acetate.

That is, the present invention relates to a laminated glass resin composition comprising 8 to 45% by weight of a multilayer structure polymer and 55 to 92% by weight of a polyvinyl acetal, wherein the multilayer structure polymer has an inner layer of 40 to 8%. 5% by weight and 60 to 15% by weight of an outer layer, wherein the inner layer contains an alkyl acrylate rubber and / or a conjugated gen rubber, and the outer layer contains an alkyl methacrylate and / or an alkyl acrylate. The present invention relates to a resin composition for laminated glass, which is a hard layer formed by polymerization.

Preferably, the polyvinyl acetal is polyvinyl butyral.

The polyvinyl acetal is preferably a plasticized polyvinyl acetal containing 10 to 45% by weight of a plasticizer.

An inner layer of the multilayer polymer is an alkyl acrylate rubber having an alkyl group having 4 to 8 carbon atoms, or an alkyl acrylate having an alkyl group having 4 to 8 carbon atoms and an aromatic bimer monomer. Polymerized It is preferable that the rubber be used. BEST MODE FOR CARRYING OUT THE INVENTION

As the polyvinyl acetal resin used in the resin composition for a laminated glass of the present invention, a polyvinyl acetal resin generally used as a main component of an interlayer film for a laminated glass can be used. More specifically, a polyvinyl butyral resin having a degree of butyralization of 60 to 70 mol% (hereinafter referred to as PVB) is preferably used as the polyvinyl acetal resin. If the degree of petitialization is less than 60 mol%, the compatibility with the plasticizer described later tends to decrease, and if the degree of petitialization exceeds 70 mol%, the PVB production process tends to require a long time. This degree of butyralization can be measured in accordance with, for example, JIS K 6728 “Polyvinyl butyral test method”.

Examples of PVB include Sekisui Chemical's Elex, Electrochemistry's Denka Butyral, Monsanto's Butvar, Hoechst's Mowital, and Picker Hemi's Pillo form.

The average polymerization degree of the PVB is preferably from 300 to 3,000, and more preferably from 1,000 to 2,000. When the average degree of polymerization is less than 300, the penetration resistance and the like of the obtained laminated glass tend to decrease, and when the average degree of polymerization exceeds 3,000, production of the interlayer film tends to be difficult. This average degree of polymerization can be measured, for example, in accordance with JIS K 6728 “Polyvinyl butyral test method”.

In the resin composition for laminated glass according to the present invention, a plasticizer can be blended into the polyvinyl alcohol as required. The plasticizer to be compounded is not particularly limited, but may be any one generally used for an interlayer. For example, triethylene glycol 2-ethylhexanoate ( 3 GO), triethylene glycol di-2-ethyl butylate (3 GH), dihexyl adipate (D HA), tetraethylene glycol diheptanoate (4 G 7), tetraethylene glycol di 2-ethyl hexanoate (4 G〇). These can be used alone or in combination of two or more.

The amount of the plasticizer to be added to the polyvinyl acetate is preferably 10 to 4

It is 5% by weight, more preferably 13 to 30% by weight. If the amount of the plasticizer is less than 10% by weight, the flexibility tends to be poor and the brittleness tends to increase during processing. If the amount exceeds 45% by weight, the degree of softening increases and the heat resistance decreases. Tend.

The multilayer structure polymer that can be used in the present invention comprises an inner layer containing an alkyl acrylate rubber and a Z or conjugated rubber, and an outer layer containing a alkyl methacrylate and / or an alkyl acrylate as a component. .

The inner layer of the multilayer polymer that can be used in the present invention includes not only an alkyl acrylate monomer and a Z or conjugated gen monomer, but also this monomer and a grafting agent and / or a crosslinking agent. Further, it can be obtained by copolymerizing another copolymerizable vinyl monomer or the like. The Tg of the copolymer (soft rubber-like material) obtained as the inner layer is preferably 15 or less. The outer layer of the multilayer polymer which can be used in the present invention comprises a polymer of an alkyl methacrylate and / or an alkyl acrylate. This outer layer is obtained by polymerizing alkyl methacrylate and Z or alkyl acrylate in the presence of 40 to 85% by weight of the soft rubber material obtained as described above as the inner layer. Can be. This polymer alone is a hard layer having a Tg of 25 ° C. or higher, and 60 to 15% by weight of the hard layer is an outer layer. The ratio of the inner layer and the outer layer of the multilayer polymer used in the present invention is preferably 40 to 85% by weight of the inner layer and 60 to 15% by weight of the outer layer, and more preferably 50 to 75% by weight of the inner layer. %, The outer layer is 50 to 25% by weight.

For the inner layer, an alkyl acrylate rubber and a conjugated diene rubber may be used in combination. In the outer layer, an alkyl methacrylate and an alkyl acrylate may be used in combination, or a monomer copolymerizable therewith may be copolymerized. It does not matter if the outer and inner layers are divided into multiple layers.

The inner layer of the multi-layer structure polymer is preferably an alkyl acrylate rubber having an alkyl group having 4 to 8 carbon atoms, or an alkyl acrylate having an alkyl group having 4 to 8 carbon atoms, if necessary. It is more preferable to contain a soft acryl-based rubbery substance obtained by copolymerizing an ester-based monomer and an aromatic vinyl monomer.

In order to improve the impact resistance without impairing the transparency of the interlayer, it is necessary to match the refractive index of the multilayer structure to the refractive index of the (plasticized) polyvinyl acetal as much as possible. is there. At this time, it is preferable that the refractive index of the entire multilayer structure polymer be close to the refractive index of the plasticized polyvinyl acetal, but the refractive index of the inner soft rubber layer alone and the refractive index of the outer hard layer alone are adjusted. However, it is more preferable to keep the refractive index of each (plasticized) polyvinyl acetal close to that of the polyvinyl acetal and to suppress the fluctuation of the refractive index inside the multilayer polymer.

Regarding the particle size of the multilayer structure polymer, generally, as the particle size of the multilayer structure polymer increases, the transparency of the resin composition using the same decreases. Therefore, the average particle size of the multilayer structure polymer used in consideration of the balance between the transparency and the degree of strength improvement is usually 500 A to 400 A, and more preferably 700 A to 300 A. 0 OA. The method for measuring the average particle size is, for example, turbidity The method by the method is convenient.

The alkyl acrylate used as the rubber component of the inner layer

Butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. Of these, butyl acrylate and 2-ethylhexyl acrylate are preferred in terms of cost and quality. Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, neoprene, and chloroprene. Usually, 1,3-butadiene is used.

Other copolymerizable vinyl monomers used as the inner layer component include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; aromatic pinyl monomers composed of styrene and its substituted products; and acrylonitrile. And vinyl cyanide compounds. Of these, alkyl methacrylate is preferred from the viewpoint of copolymerizability.

Furthermore, by using a silicon-based monomer as a soft component, an inner layer with a lower T g can be obtained.

The grafting agent used in the present invention has an unsaturated bond having different reactivity in the molecule, and specific examples include aryl methacrylate.

The cross-linking agent used in the present invention contains a plurality of unsaturated groups having the same reactivity, and specific examples thereof include dibielbenzene.

Examples of the alkyl methacrylate and alkyl acrylate used as the outer layer component include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and the like. . Above all, rubber with low penetration into rubber Alkyl methacrylate is preferred in that it coats the surface of the polymer. As the monomer copolymerizable with the alkyl methacrylate and / or the alkyl acrylate as the outer layer component, various vinyl monomers can be arbitrarily used. Examples of the biel monomer include, but are not limited to, aromatic vinyl monomers composed of styrene and a substituted product thereof; vinyl cyanide conjugates such as acrylonitrile; and maleic anhydride, maleic acid, and maleic anhydride. And unsaturated dicarboxylic acid compounds such as acid monoalkyl esters, maleic acid dialkyl esters, fumaric acid, fumaric acid monoalkyl esters, and fumaric acid dialkyl esters. The copolymerizable monomer can be arbitrarily used as long as it is copolymerizable. For example, in order to improve the affinity with polyvinyl acetal, a relatively special monomer is used. It is also possible to use monomers.

The compounding amount of the multilayer polymer in the (plasticized) polyvinyl acetal is preferably 8 to 45% by weight, more preferably 10 to 30% by weight. If the amount is less than 8% by weight, sufficient strength cannot be obtained, and if the amount exceeds 45% by weight, the transparency of the obtained composition tends to decrease.

The method for producing the multilayer polymer is not particularly limited, and any polymerization method can be used, but an emulsion polymerization method is particularly preferred.

In the resin composition for laminated glass of the present invention, a magnesium (Mg) salt and / or a potassium (K) salt are added to the (plasticized) polyvinyl acetal resin film as an adhesive force adjuster. Preferably, it is added so as to contain 0.000 ppm. If the added amount is less than 10 ppm, the adhesive force controlling power tends to be insufficient, and if it exceeds 500 ppm, insoluble mass tends to be generated. Such an adhesion regulator is not particularly limited, and examples thereof include organic acid metal salts of organic acid magnesium salts and organic acid potassium salts. Among them, carboxylic acid magnets having 1 to 28 carbon atoms Preferred are sodium salts, and more preferred are magnesium acetate, magnesium propionate, magnesium 2-ethylbutanoate, magnesium 2-ethylhexanoate and the like. These can be used alone or in combination of two or more.

A modified silicone oil can also be used in combination with this adhesive force adjusting agent as another adhesive force adjusting agent. Examples of the modified silicone oil include ether-modified silicone oil, epoxy-modified silicone oil, ester-modified silicone oil, and amine-modified silicone oil. These are generally viscous liquids obtained by reacting the compound to be modified with polysiloxane. The added amount of the modified silicone oil is preferably 0.05 to 0.5% by weight, and more preferably 0.02 to 0.2% by weight. If the amount of the modified silicone oil is less than 0.05% by weight, the combined effect is unlikely to be exhibited, and if it exceeds 0.5% by weight, the appearance such as transparency may be impaired.

The resin composition for a laminated glass of the present invention may further comprise, if necessary, a stabilizer (for example, an antioxidant, an ultraviolet absorber, etc., as long as the effects of the present invention are not impaired). Stabilizers), plasticizers, lubricants, flame retardants, release agents, antistatic agents, antibacterial and antifungal agents and the like may be added. Specific examples include triphenyl phosphite and dibutyltin maleate as stabilizers; paraffinic oil, polybutene-based oil, light oil, spindle oil, machine oil, amaji oil, sesame oil, castor oil as plasticizers. Oil, camellia oil, octyl phthalate, dibutyl phthalate, octyl adipate, tricresyl phosphate, etc .; lubricants such as polyethylene wax, polypropylene wax, montanic acid resins, etc .; Fate, deca-mouth mobiphenyl, decabromobiphenyl ether, And antimony trioxide.

Laminated glass using the resin composition for laminated glass of the present invention can be produced, for example, as follows. The components contained in the resin composition of the present invention are melt-kneaded under heating conditions, and a film is produced by a method such as pressing or extrusion. The resulting film is sandwiched between two glass sheets and pressed at normal temperature by passing between rubber rolls. After that, pressurization is performed again by a rubber roll while heating to 70 to 80 ° C. The pre-adhesives obtained in this manner are subjected to a temperature of 130 to 150 ° C and a pressure of 10 to 20 kg / cm2 for 10 to ²⁰ minutes using a pneumatic autoclave or the like. It is manufactured by performing actual bonding after processing.

The type of the above glass is not particularly limited, and examples thereof include various inorganic glasses such as float glass, polished glass, and template glass, and organic glass. The thickness of the glass is not particularly limited and may be appropriately selected depending on the application. In practice, however, the thickness is preferably 2.0 to 4.0 mm.

Next, the present invention will be described in more detail based on examples, but the present invention is not limited to only these examples.

In the examples, “%” and “parts” mean by weight unless otherwise specified.

Example 1

A multilayer polymer was prepared as follows. In a glass reactor equipped with a thermometer, stirrer, reflux cooler, nitrogen inlet device, and monomer and emulsifier addition device, 200 parts of distilled water, 0.5 part of potassium stearate, and 0.5 parts of formaldehyde sulfoxylic acid Charge 0.2 parts of sodium, 0.01 parts of ethylenediaminetetraacetic acid2Na salt, and 0.05 parts of ferrous sulfate7 hydrate, and stir in a nitrogen stream at 60 ° C. The temperature rose. Then, 68.8 parts of butyl acrylate, 11.2 parts of styrene, 0.8 parts of acryl methacrylate and A monomer mixture consisting of 0.1 part of peroxide at the menhide port was added dropwise over 4 hours. Along with the addition of the monomer mixture, 2 parts of a 5% by weight aqueous solution of potassium stearate was added continuously over 4 hours. After the addition of the monomer mixture, stirring was continued for 1.5 hours, and then 13 parts of methyl methacrylate, 7 parts of butyl acrylate, and 0.01 part of cumene hydroboxide were continuously used as a graft monomer component for 1 hour. Was added. After the addition was completed, 0.01 parts of peroxide of cumene hydride was added, and the mixture was further stirred for 2 hours to complete the polymerization. The conversion was 99.8%. The obtained graft copolymer latex (multilayer structure polymer) was salted out and coagulated with an aqueous solution of calcium chloride, heat-treated, and then dehydrated and dried to obtain a white powdery resin. The average particle size of this resin was 180 OA as measured by a turbidity method. As the polyvinyl acetal resin, PVB having a degree of butyralization of 68 mol%, a vinyl acetate component of 1 mol%, and a polymerization degree of 20000 was used. With respect to 100 parts of this PVB, 15 parts of the above-mentioned polymer having a multilayer structure, —35 parts of ethyl hexanoate is added, and 500 ppm of magnesium acetate is further added. The mixture is melt-kneaded, and then press-formed at 150 at 30 ° C using a press-forming machine for laminated glass having an average film thickness of 0.40 mm. An intermediate film was obtained. The obtained intermediate film is sandwiched between transparent 2.5 mm-thick float glasses from both sides, placed in a rubber bag, degassed at a vacuum of 3.0 kPa for 20 minutes, and then left as it is. It was transferred to a 90 oven and held for 30 minutes. The laminated glass thus preliminarily bonded was hot-pressed in an air type autoclave at a temperature of 140 T and a pressure of 1.5 MPa for 20 minutes to obtain a laminated glass.

Example 2

Example 1 was carried out in the same manner as in Example 1 except that 35 parts of triethylenedalichol di-2-ethylhexanoate was not added. Example 3

In the preparation of the multilayer polymer, 68.8 parts of butyl acrylate and 11.2 parts of styrene were converted to 76 parts of butyl acrylate in the polymerization of the soft layer, and 13 parts of methyl methacrylate, a component of the hard layer, and A multilayer polymer was obtained in the same manner as in Example 1 except that methyl methacrylate was changed to 20 parts and butyl acrylate was changed to 4 parts instead of 7 parts of butyl acrylate. The particle size was 175 OA.

Comparative Example 1

As a polyvinyl acetal resin, PVB having a degree of butyralization of 68 mol%, a vinyl acetate component of 1 mol%, and a degree of polymerization of 2000 was used. Triethylene glycol di-2-ethyl was added to 100 parts by weight of this PVB. After adding 40 parts by weight of xananoate, then adding 500 ppm of magnesium acetate, and melt-kneading, the mixture was press-formed at 150 using a press-forming machine for 30 minutes. An interlayer of 40 mm for laminated glass was obtained. Except for this, a laminated glass was obtained in the same manner as in Example 1.

(Evaluation method)

The laminated glass of 30 O mm X 30 O mm obtained in the example and the comparative example was placed on a cylindrical cylinder having a diameter of 25 O mm, and a steel ball having a mass of 100 g was vertically moved upward by 5 m. It was dropped further and the destruction state was observed. Using Comparative Example 1 as a blank, the state of breakage and the glass peeling property were observed. Examples 1 to 3 were less susceptible to breakage and less glass peeling than Comparative Example 1.

From the above, it is clear that a resin composition comprising a multilayer polymer having a rubber component as an inner layer and a plasticized polyvinyl acetal is effective as a material for an interlayer film for laminated glass. Industrial applicability The resin composition obtained by the present invention has adhesiveness to glass and good breaking strength and elongation, and a laminated glass manufactured using this has good penetration resistance. A material suitable for a resin composition for glass is used.

Claims

Scope of Word

1. A resin composition for laminated glass comprising 8 to 45% by weight of a polymer having a multilayer structure and 55 to 92% by weight of a polybiacetal, wherein the polymer having a multilayer structure has an inner layer of 40 to 85%. % By weight and an outer layer of 60 to 15% by weight. The inner layer contains an alkyl acrylate rubber and Z or a conjugated diene rubber, and the outer layer is an alkyl methacrylate and / or an alkyl acrylate. A resin composition for laminated glass, which is a hard layer obtained by polymerizing the above.

2. The resin composition for laminated glass according to claim 1, wherein the polypinyl acetal is polyvinyl butyral.

3. The resin composition for laminated glass according to claim 1, wherein the polyvinyl acetal is a plasticized polyvinyl acetal containing 10 to 45% by weight of a plasticizer.

4. The inner layer of the multi-layer polymer has an alkyl acrylate rubber having an alkyl group having 4 to 8 carbon atoms, or an alkyl acrylate having an alkyl group having 4 to 8 carbon atoms and an aromatic vinyl monomer. 2. The resin composition for laminated glass according to claim 1, wherein the resin composition is a rubber obtained by polymerizing a rubber.