JPH06206739A - Adhesive resin for producing laminated glass - Google Patents

Abstract

PURPOSE:To obtain an adhesive resin for producing laminated glass having excellent optical uniformity and transparency, keeping high softness, heat- resistance and penetration resistance over a wide temperature range, exhibiting low polymerization shrinkage and capable of producing various kinds of laminated glass by compounding a specific polymerizable (meth)acrylate oligomer. CONSTITUTION:A resin for laminated glass is incorporated with 5-70wt.% of a polymerizable (meth)acrylate oligomer having a numberaverage molecular weight of 500-100,000 and containing >=1.5mol of a radically polymerizable functional groups based on one molecule on an average. The oligomer is produced by introducing a (meth)acryloyl group (e.g. by converting a carboxyl group) into an oligomerized monomer mixture composed mainly of (meth) acrylate monomer. The resin for laminated glass may be cured at normal temperature in the production of a laminated glass, however, it may be heated with hot air for example in the case of a low room temperature. The polymerization initiator for cold-curing is preferably an organic peroxide or an azo compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive resin for producing laminated glass, which comprises a polymerizable monomer curable at room temperature in the production of laminated glass.

[0002]

2. Description of the Related Art A laminated glass material obtained by stacking and adhering a plurality of glass plates or plastic plates has excellent soundproofing, safety, anti-scattering properties, heat insulating properties, etc. Accordingly, it is possible to impart excellent properties such as ultraviolet cut property, infrared cut property, and design property, and therefore it is widely used in the fields of building materials, automobiles, cathode ray tubes and the like. Conventional laminated glass has been manufactured by sandwiching an interlayer film made of, for example, plasticized polyvinyl butyral between a plurality of glass plates, degassing, and then pressing. However, such conventional manufacturing methods not only have poor workability such as cleaning and cutting of the film, but also because it is necessary to put the whole in a bag, degas, and temporarily bond it, and then pressurize it in an autoclave. However, there is a problem that the cost is low and the cost is high, and there is a drawback that a larger plate cannot be manufactured.

On the other hand, as a method for producing a laminated glass, a plurality of glass plates or plastic plates are superposed with a spacer serving as a sealing member sandwiched therebetween, and a liquid adhesive is placed in a cavity formed between the plate materials. A method of manufacturing by injecting and curing has been proposed. As a curing method, a method of curing by irradiation with ultraviolet rays or radiation in the presence of a photopolymerization initiator has been proposed, but there is a problem in that it is difficult to obtain a laminated glass having an ultraviolet blocking function or a dark laminated glass. A highly transparent (meth) acrylate monomer composition is used as a liquid adhesive to be injected into the cavity, but a liquid composition containing only a (meth) acrylate monomer has a large polymerization shrinkage ratio. ,
There is a problem that distortion is likely to occur and cracking is likely to occur when the deformed glass, especially the bent glass or the large-sized laminated glass, especially the glass plate, has a large thickness.

Therefore, a technique of blending a (meth) acrylate (co) polymer in a monomer composition to be injected to alleviate the polymerization shrinkage ratio was also examined (Japanese Patent Publication No. 62-4345).
No. 2, JP-A-2-97439), since the (co) polymer blended here no longer has a polymerizable group, it will be present as a block-like foreign substance in the polymerization product of the monomer component,
It may adversely affect the optical uniformity and cause clouding. On the other hand, a method using a polymer having reactivity has also been proposed (JP-A-52-59617, JP-A-53-59778,
JP-A-63-281101, etc.). The components of the reactive polymer used in these methods are polyurethane, polyester,
It is limited to polyethers and unsaturated polyolefins. For example, polyurethane and unsaturated polyolefins do not have sufficient light (weather) resistance, and polyesters and polyethers have insufficient water (wet) resistance and transparency. There was a problem in terms of reliability, such as when it became worse. In particular, the current laminated glass is often used in fields where replacement after construction is not intended, and insufficient light (weather) resistance and water (wet) resistance are considered to be fatal defects.

[0005]

The adhesive resin used in the production of laminated glass preferably has a glass transition point lower than room temperature in terms of safety and anti-scattering property. Therefore, when the resin is used at room temperature or higher, for example, 40 ° C. or higher, the resin may become too soft and the performance as a laminated glass such as penetration resistance and soundproofing properties may not be sufficiently exhibited. On the other hand, when the glass transition point of the resin is raised to around room temperature, the flexibility of the resin itself becomes insufficient, and there is a problem that impact resistance and shatterproof property at the time of breakage deteriorate.

The present invention has been made in view of the above circumstances, solves the above problems, is excellent in optical uniformity and transparency, and has flexibility, heat resistance and penetration resistance in a wide temperature range. In order to provide an adhesive resin for producing laminated glass (hereinafter simply referred to as a resin for laminated glass) that retains the above properties and has a low polymerization shrinkage ratio during the production of laminated glass, and can be applied to the production of various types of laminated glass. To do.

[0007]

Means for Solving the Problems According to the present invention which has achieved the above object, an adhesive resin for producing a laminated glass has a number average molecular weight of
The gist of the present invention is to contain 5 to 70% by weight of a polymerizable (meth) acryl oligomer having an average of 1.5 or more radically polymerizable polymerizable functional groups per molecule at 500 to 100,000.

[0008]

The above-mentioned "polymerizable (meth) acrylic oligomer having a number average molecular weight of 500 to 100,000 and having an average of 1.5 or more radically polymerizable polymerizable functional groups per molecule" (hereinafter referred to as reactive oligomer) means When the resin for laminated glass is polymerized and cured, it can be radically copolymerized together. By making the constituents of the reactive oligomer to be (meth) acrylic, reliability with respect to light (weather) resistance and water (wet) resistance can be maintained. Further, by providing the oligomer with radical polymerizability, optical uniformity can be maintained even when a block polymer unit of a different component is introduced. For example, polymer components having different glass transition points can be used. Can also be introduced. Therefore, when a laminated glass is produced using a monomer composition containing a reactive oligomer having a relatively low Tg, such as butyl acrylate, 2-ethylhexyl acrylate, and lauryl (meth) acrylate as a main component, it is flexible in a low temperature range. When a laminated glass is made using a reactive oligomer whose main component is methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, etc., which has a relatively high Tg, it is possible to improve the heat resistance and anti-scattering property. Even in the above atmosphere, the resin does not become too soft, and it is possible to obtain a laminated glass in which penetration resistance and sound insulation do not easily deteriorate.

The reactive oligomer according to the present invention is not particularly limited as long as it has 1.5 or more radically polymerizable polymerizable functional groups per molecule. If the number of polymerizable functional groups per molecule is less than 1.5, the resin may not be uniform, and the resin may become cloudy. When the molecular weight per functional group is less than 500, the effect of relaxing the polymerization shrinkage is low, and when the molecular weight per functional group exceeds 8000, scattered light may appear and turbidity may occur.

The number average molecular weight of the reactive oligomer according to the present invention is 500 to 100000, preferably 1000 to 3000.
0 (hereinafter, the number average molecular weight in the present invention means GP
It is polystyrene conversion in C). Number average molecular weight is
If the reactive oligomer is less than 500, the physical properties of the polymer unit portion of the oligomer are difficult to be expressed, and the relaxation effect of the polymerization shrinkage is low, and a polymerizable monomer composition that can be cured at room temperature when the number average molecular weight exceeds 100,000. In such a case, the viscosity becomes high, which makes it difficult to perform processing operations such as injection and defoaming during the production of laminated glass.

The content of the reactive oligomer in the resin for laminated glass according to the present invention is preferably 5 to 70% by weight. When the amount is less than 5% by weight, the effect of modifying the mechanical properties and the like by the reactive oligomer is difficult to be exhibited, and the low shrinkage effect is difficult to be obtained. When the amount is more than 70% by weight, the viscosity of the resin for laminated glass increases, Processing work during glass manufacturing becomes difficult.

The reactive oligomer according to the present invention is not particularly limited as long as it is a product obtained by oligomerizing a monomer mixture containing a (meth) acrylate monomer as a main component and adding a (meth) acryloyl group. . Exemplifying the method for producing a reactive oligomer of the present invention, preferably, a pre-reactive oligomer is synthesized by an oligomerization reaction in the presence of a chain transfer agent. This pre-reactive oligomer is easily converted to a (meth) acryloyl group such as a carboxyl group, a hydroxyl group, an epoxy group, an isocyanato group derived from a chain transfer agent having a functional group or a polymerizable monomer having a functional group. It has 1.5 or more convertible groups per molecule.
If necessary, this pre-reactive oligomer is treated with glycidyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate in the presence of a catalyst to make it polymerizable. Reactive oligomers with rich (meth) acryloyl groups. The reactive oligomer according to the present invention contains 50% by weight or more of monofunctional (meth) acrylate as a constituent. As the copolymerization component, (meth) acrylic acid, (meth) acrylamides, aromatic vinyl compounds and the like can be used.

The monomer component in the polymerizable monomer composition used for the resin for laminated glass according to the present invention is not particularly limited. However, when a polymerizable monomer that is copolymerized with the above-mentioned reactive oligomer is used, it is possible to obtain better optical homogeneity, and such a monomer is a monofunctional (meth) acrylate monomer. And a polyfunctional (meth) acrylate monomer can be used. Examples of the monofunctional (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate. , 2-methoxyethyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and the like can be used, and examples of the polyfunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate. Acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexamethylene glycol di ( Data) acrylate, and trimethylolpropane tri (meth) acrylate.

The laminated glass resin according to the present invention preferably has a crosslinked structure. By having a crosslinked structure, it is possible to maintain the integrity of the adhesive glass plate even in a high temperature region while maintaining the flexibility near room temperature, and the composite glass plate does not shift. It is recommended to use a polyfunctional (meth) acrylate monomer in addition to the above-mentioned reactive oligomer as a component for imparting the crosslinked structure. The amount of the polyfunctional (meth) acrylate monomer used varies depending on the physical properties of the resin obtained, the amount of the reactive oligomer used, the molecular weight and the number of functional groups, but when the reactive oligomer is used in an amount of 5 to 20% by weight. 1 to 20% by weight is preferable, and when the reactive oligomer is used at 20 to 70% by weight, it is preferably 5% by weight or less.

As a method for producing a laminated glass using the resin for laminated glass according to the present invention, it is possible to cure it at room temperature, but warm it by heating it with warm air even when the room temperature is low. Good. As the room temperature-curable polymerization initiator according to the present invention, it is preferable to use an organic peroxide or an azo compound, and it is preferable to add a metal salt, a complex, a quaternary ammonium salt, a thiol or the like for activation. Examples of the organic peroxide used in the present invention include t-butylperoxypivalate, t-butylperoxyneodecanate, t-butylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, Examples of the azo compound include lauroyl peroxide and the like.
2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile), 2 , 2'-azobis (2-methylbutyronitrile) and the like. As the metal salt or complex used in the present invention, a copper compound or a vanadium compound is preferable because the transparency of the obtained resin can be maintained. As the copper compound, those which are easily dissolved in the (meth) acrylate monomer are preferable, and examples thereof include copper naphthenate and copper acetylacetonate. Examples of the vanadium compound include VN-2 (manufactured by Kayaku Akzo Co., Ltd.) and vanadium acetylacetonate. The quaternary ammonium salt used in the present invention is preferably one that is uniformly dissolved in the (meth) acrylate monomer. A liquid or liquid at room temperature is preferable for uniform dissolution, and examples thereof include trioctylmethylammonium chloride and trioctylmethylammonium bromide.

It is preferable to add a plasticizer to the polymerizable monomer composition used for the laminated glass resin according to the present invention in order to reduce the polymerization shrinkage and to impart flexibility to the resin. The plasticizer is not particularly limited as long as it is compatible with the polymerizable monomer composition, and a phosphoric acid type such as tributyl phosphate, a phthalic acid type such as dioctyl phthalate,
It is possible to use adipic acid-based plasticizers such as dibutyl adipate and isononyl adipate, and oxyester-based plasticizers such as tributyl acetylcitrate.

Further, as a polymerizable monomer composition of a resin for laminated glass containing the reactive oligomer according to the present invention,
In addition to (meth) acrylate monomers, other monomers copolymerizable with them, polymers, silane coupling agents, adhesion improvers, chain transfer agents, ultraviolet absorbers, infrared absorbers,
It is also free to appropriately contain a photochromic compound, a drip-proofing agent and the like.

[0018]

EXAMPLES Examples according to the present invention will be described below. The methods for evaluating physical properties in the following examples are as follows. (Appearance) The hue and transparency of the obtained sheet-shaped laminated glass were visually observed, and those which are colorless and transparent and show no distortion due to polymerization shrinkage are indicated by “◯”. Other than that, the state was shown. (Workability) In the work of injecting into the cavity, those that are easy to inject and easy to perform defoaming treatment are indicated by "○". In addition, for items that are difficult to defoam and have poor workability, “×”
Indicated by. (Curability) Those that were completely cured within 15 hours are indicated by "○". (Adhesiveness) The adhesiveness with the glass plate and the adhesiveness after 100 cycles of the cooling and heating cycle of -20 ° C and 80 ° C were visually observed, and those having no abnormality were indicated by "○". In addition, the occurrence of peeling is indicated by "x". Reactive oligomers A to H used in Examples were prepared in Reference Examples 1 to 8 below and provided for Examples.

Reference Example 1 In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen gas blowing tube, 280 parts by weight of methyl methacrylate, 17.2 parts by weight of methacrylic acid, 10.6 parts by weight of β-mercaptopropionic acid, After 150 parts by weight of toluene and 0.3 parts by weight of 2,2'-azobis (isobutyronitrile) were charged and sufficiently replaced with nitrogen gas, the reaction solution was heated to 80 ° C and kept at the same temperature for 8 hours. After the reaction solution was once cooled, 51 parts by weight of glycidyl methacrylate, 1.0 part by weight of N, N-dimethyllaurylamine and 0.3 part by weight of 4-methoxyphenol were added. The reaction solution was heated to 105 ° C. and kept at the same temperature for 6 hours. After cooling, it was reprecipitated from methanol to obtain a reactive oligomer A. The number average molecular weight of this reactive oligomer A is 6600, and the number of polymerizable functional groups per molecule is 4.2.
It was an individual.

Reference Examples 2 to 7 Reactive oligomers B to G were obtained in the same manner as in Reference Example 1, except that the monomer composition and the like were changed as shown in Table 1 in the same apparatus as in Reference Example 1. It was

Reference Example 8 104 parts by weight of styrene, 176 parts by weight of methyl methacrylate and methacrylic acid were placed in a 5-necked flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen gas blowing tube and a dropping funnel.
6 parts by weight, 0.4 parts by weight of β-mercaptopropionic acid, 100 parts by weight of toluene, 0.3 parts by weight of 2,2'-azobis (isobutyronitrile) were charged, and after sufficiently replacing with nitrogen gas, the reaction solution was heated to 80 ° C. The temperature was raised. At the same temperature, a solution prepared by previously dissolving 3.8 parts by weight of β-mercaptopropionic acid in 170 parts by weight of toluene was added dropwise from a dropping funnel over 6 hours. The temperature was maintained at the same temperature for 2 hours. After the reaction solution was once cooled, 20 parts by weight of glycidyl methacrylate, 1.0 part by weight of N, N-dimethyllaurylamine and 0.2 part by weight of 4-methoxyphenol were added. The temperature of the reaction solution was raised to 105 ° C, and 6
The temperature was kept the same for the time. After cooling, it was reprecipitated from methanol to obtain a reactive oligomer H. The number average molecular weight of this reactive oligomer H was 5,400 and the number of polymerizable functional groups per molecule was 2.8.

[0022]

[Table 1]

Example 1 30 parts by weight of the reactive oligomer A obtained in Reference Example 1, 15 parts by weight of 2-ethylhexyl methacrylate, 18 parts by weight of 2-ethylhexyl acrylate, 20 parts by weight of butyl acrylate, 2 parts by weight of tetraethylene glycol dimethacrylate, A polymerizable monomer composition consisting of 15 parts by weight of isononyl adipate, 0.05 part by weight of trioctylmethylammonium chloride, 0.5 part by weight of γ-mercaptopropyltrimethoxysilane, 0.2 part by weight of a 1% by weight solution of copper naphthenate in methyl methacrylate. And t-butylperoxy-2
-1.5 parts by weight of ethyl hexanoate were added. This polymerizable composition was poured and sealed in a cavity (thickness 1 mm) formed by stacking two 300 mm × 300 mm × 3 mm glass sheets and sealing the peripheral portion with a spacer. The glass material was left standing at room temperature for 10 hours to carry out a polymerization reaction to prepare a laminated glass material. The obtained laminated glass material was colorless and transparent, and no distortion was observed. The physical properties are shown in Table 2.

Examples 2 to 9 In Example 1, the polymerizable monomer composition, additives, etc. are shown in Table 2.
In the same manner as in Example 1 except that the replacement is performed as shown in
Laminated glass materials 2-9 were obtained. The physical properties thereof are also shown in Table 2.

Comparative Examples 1 to 5 Comparative laminated glass materials 1 to 1 were prepared in the same manner as in Example 1 except that the polymerizable monomer composition, additives and the like in Example 1 were changed as shown in Table 3. Got 5. The physical properties thereof are also shown in Table 3.

[0026]

[Table 2]

[0027]

[Table 3]

The abbreviations shown in Tables 1, 2, and 3 are as follows. MMA: methyl methacrylate BA: butyl acrylate 2EHMA: 2-ethylhexyl methacrylate 2EHA: 2-ethylhexyl acrylate 4EG: tetraethylene glycol dimethacrylate St: styrene GMA: glycidyl methacrylate HEMA: 2-hydroxyethyl methacrylate HEA: 2-hydroxyethyl acrylate IEMA: 2-isocyanatoethyl methacrylate MAA: methacrylic acid AA: acrylic acid βMPA: β-mercaptopropionic acid DM: dodecyl mercaptan ME: 2-mercaptoethanol AIBN: 2,2′-azobis (isobutyronitrile) DMLA: N, N -Dimethyllaurylamine DBTL: dibutyltin dilaurate DINA: isononyl adipate EH: t-butylperoxy 2-ethylhexanoate TOMAC: trioctylmethylammonium chloride MPTMS: γ-mercaptopropyltrimethoxysilane Cu: 1% by weight solution of copper naphthenate in methylmethacrylate VN2: vanadium complex (Kayaku Akzo Co., Ltd.) J: Methyl methacrylate polymer (number average molecular weight 9000) K: Reactive oligomer K (methacryloyl group-terminated methyl methacrylate polymer, number average molecular weight 9000, 0.95 polymerizable functional groups / molecule) L: Reactive oligomer L ( Methacryloyl group-terminated methyl methacrylate polymer, number average molecular weight 180,000,
Polymerizable functional group 5.8 / molecule) M: trimethylolpropane trimethacrylate (molecular weight 338, polymerizable functional group 3.0 / molecule)

As shown in Tables 2 and 3, Comparative Example 1
Uses a methylmethacrylate polymer instead of the reactive oligomer, and therefore has no polymerizable functional group, and therefore has insufficient optical uniformity and white turbidity is observed in the appearance evaluation. In Comparative Example 2, a methacryloyl group-terminated methyl methacrylate polymer was used as the reactive oligomer K, but since the number of polymerizable functional groups was only 0.95 per molecule, the uniformity of the resin was insufficient and clouding occurred as in Comparative Example 1. ing. In Comparative Example 3, since the reactive oligomer is omitted, the polymerization shrinkage rate is large, and the appearance is distorted. In Comparative Example 4, methacryloyl group-terminated methyl methacrylate polymerization was used as the reactive oligomer L, but the number average molecular weight was
Since it is as large as 180000, its appearance and workability are poor. In Comparative Example 5, trimethylolpropane trimethacrylate having a molecular weight of 338 is used, but its appearance and adhesion are poor. On the other hand, all of Examples 1 to 9 have obtained good evaluation.

[0030]

EFFECTS OF THE INVENTION Since the present invention is constituted as described above, even if an oligomer having different constituents from each other is copolymerized in a resin, optical uniformity and transparency can be maintained, and therefore, heat resistance can be improved. It is possible to introduce a unit having a high glass transition point, which is effective for improvement, or to incorporate a rubber polymer having a low glass transition point. Therefore, it has become possible to provide an adhesive resin for producing a laminated glass, which is capable of imparting heat resistance and soundproofing property functions, and can also alleviate the polymerization shrinkage rate during production.

Claims (1)

[Claims] 1. A polymer having a number average molecular weight of 500 to 100,000 and containing 5 to 70% by weight of a polymerizable (meth) acrylic oligomer having an average of 1.5 or more radically polymerizable polymerizable functional groups per molecule. Adhesive resin for production of laminated glass characterized by