JP6635933B2 - Laminated glass and interlayer for laminated glass - Google Patents

Description

  One embodiment of the present invention relates to a laminated glass and an interlayer for a laminated glass.

  Lighting windows, partitions, bathroom doors, and the like are required to transmit light, but to be invisible to persons and objects behind them. Examples of building materials having such performance include, for example, glass (ground glass) having fine irregularities on its surface and smoked laminated glass having a milky white resin layer (intermediate film) between two transparent glasses. No.

JP-A-59-64550 discloses a smoked laminated glass in which a translucent opacifier is dispersed in a thermoplastic resin to form an intermediate layer. Japanese Patent Application Laid-Open No. 7-157341 discloses an intermediate film obtained by adding titanium dioxide to a composition comprising an ethylene-vinyl ester copolymer and a thermoplastic polymer incompatible with a modified product thereof. ing.
JP-A-6-263489 discloses a milky white laminated glass having a milky white laminated glass interlayer composed of a polyvinyl acetal resin having a different degree of saponification and a plasticizer.

However, the intermediate layer described in JP-A-59-64550 and the intermediate films described in JP-A-7-157341 and JP-A-6-263489 are exposed to a high-temperature and high-humidity environment for a long time. As a result, water penetrates from the edge of the film or the like, and the inside of the film deteriorates, and the light transmittance tends to be unable to be maintained. Therefore, a laminated glass having performance (water resistance) in which deterioration is suppressed even when exposed to a high-temperature and high-humidity environment for a long period of time, and light transmittance and blindness has not yet been provided. is there.
Note that the blindfolding property means a performance in which a person and an object on the opposite side of the laminated glass from the viewing side cannot be visually recognized from the viewing side of the laminated glass.

One embodiment of the present invention has been made in view of the above, and aims to achieve the following objects.
That is, an object of one embodiment of the present invention is to provide a laminated glass and an interlayer film for a laminated glass that are excellent in light transmittance, blindness, and water resistance.

Specific means for achieving the above object include the following aspects.
<1> Two glasses, and at least one copolymer selected from an ethylene / unsaturated carboxylate ester copolymer and an ethylene / vinyl ester copolymer disposed between the two glasses, and an ethylene-based copolymer. An intermediate film including an A film containing a polymer (excluding the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer), and having a haze of 50% or more and 99.5 or more. % Or less, and the total light transmittance is 50% or more and 90% or less.
<2> The B film, wherein the intermediate film contains at least one copolymer selected from an ethylene / unsaturated carboxylic acid copolymer and an ionomer of an ethylene / unsaturated carboxylic acid copolymer; The laminated glass according to <1>, which has a multilayer structure in which at least three films having the A film disposed between two B films are stacked.
<3> The laminated glass according to <2>, wherein the B film further contains a silane coupling agent.
<4> The ethylene / unsaturated carboxylic acid ester copolymer is an ethylene / (meth) acrylate copolymer, and the ethylene / vinyl ester copolymer is an ethylene / vinyl acetate copolymer; The copolymer according to any one of <1> to <3>, wherein the copolymer is at least one copolymer selected from an ethylene / unsaturated carboxylic acid copolymer and an ionomer of the ethylene / unsaturated carboxylic acid copolymer. The laminated glass as described.
<5> In the ethylene-unsaturated carboxylic acid copolymer contained in the A film, the content of the structural unit derived from the unsaturated carboxylic acid is 1% by mass to 10% by mass based on the total mass of the copolymer. <4> is a laminated glass according to <4>.
<6> the total content of the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer is the ethylene / unsaturated carboxylic acid ester copolymer, the ethylene / vinyl ester copolymer, And at least 5% by mass and less than 45% by mass with respect to the total mass of the ethylene-based polymer, wherein the content of the ethylene-based polymer is the ethylene / unsaturated carboxylic acid ester copolymer, the ethylene / vinyl ester The laminated glass according to any one of <1> to <5>, which is more than 55% by mass and 95% by mass or less based on the total mass of the copolymer and the ethylene-based polymer.
<7> At least one copolymer selected from an ethylene / unsaturated carboxylic acid ester copolymer and an ethylene / vinyl ester copolymer, and an ethylene polymer (provided that the ethylene / unsaturated carboxylic acid ester copolymer And excluding the ethylene / vinyl ester copolymer), the haze at a thickness of 400 μm is 50% or more and 99.5% or less, and the total light transmittance is 50% or more and 90% or more. The following interlayer film for laminated glass.

  According to one embodiment of the present invention, there is provided a laminated glass and an interlayer film for a laminated glass having excellent light transmittance, blindness, and water resistance.

4 is a photograph showing a state of a sample after a water resistance evaluation is performed on the laminated glass sample of Comparative Example 1.

<Interlayer for laminated glass>
The laminated glass comprises at least one copolymer selected from an ethylene / unsaturated carboxylic acid ester copolymer and an ethylene / vinyl ester copolymer, and an ethylene-based polymer (provided that the ethylene / unsaturated carboxylic acid ester copolymer And an intermediate film for laminated glass (hereinafter, also simply referred to as an intermediate film) including an A film containing a polymer and the ethylene / vinyl ester copolymer).
The intermediate film has a haze of 50% or more and 99.5% or less and a total light transmittance of 50% or more and 90% or less at a thickness of 400 µm.
The intermediate film was disposed between the two B films, including two B films containing at least one selected from an ethylene / unsaturated carboxylic acid copolymer and an ionomer of the ethylene / unsaturated carboxylic acid copolymer. It is preferable to have a multilayer structure in which at least three films including the film A are stacked.

  (Meth) acrylic acid in this specification is meant to include both acrylic acid and methacrylic acid.

The reason why the effect of the embodiment of the present invention appears is not clear, but is presumed as follows.
That is, in one embodiment of the present invention, the A film included in the interlayer film of the laminated glass is made of an ethylene / unsaturated carboxylic acid ester copolymer and an ethylene / vinyl ester copolymer having high light transmittance and different refractive indices. By including at least one selected copolymer and an ethylene-based polymer (however, excluding the ethylene-unsaturated carboxylic acid ester copolymer and the ethylene-vinyl ester copolymer) It is considered that the intermediate film as a whole becomes milky white from the difference in refractive index between the two while maintaining the light transmittance, and expresses the blinding property.
Further, since the A film contains an ethylene-based polymer (however, excluding the ethylene-unsaturated carboxylic acid ester copolymer and the ethylene-vinyl ester copolymer), the interlayer film is also excellent in water resistance. It is thought to be something.

  Hereinafter, the A film included in the intermediate film will be described in detail.

≪A film≫
The intermediate film is made of at least one copolymer selected from an ethylene / unsaturated carboxylic acid ester copolymer and an ethylene / vinyl ester copolymer, and an ethylene-based polymer (provided that the ethylene / unsaturated carboxylic acid ester copolymer is used). (Except for the polymer and the ethylene / vinyl ester copolymer)).
When the intermediate film includes the A film, the entire intermediate film is excellent in light transmittance, blindfold, and water resistance.
The A film may contain a resin other than the ethylene / unsaturated carboxylic acid ester copolymer, the ethylene / vinyl ester copolymer, and the ethylene-based polymer, if necessary.

[Ethylene / unsaturated carboxylic acid ester copolymer]
The A film contains at least one copolymer selected from an ethylene / unsaturated carboxylic acid ester copolymer and an ethylene / vinyl ester copolymer described below.
The ethylene / unsaturated carboxylic acid ester copolymer contains at least a structural unit derived from ethylene and a structural unit derived from an unsaturated carboxylic acid ester. The ethylene / unsaturated carboxylic acid ester copolymer may be a random copolymer, a block copolymer, or an alternating copolymer.

Examples of the structural unit derived from an unsaturated carboxylic acid ester include a structural unit derived from an unsaturated carboxylic acid alkyl ester.
As the unsaturated carboxylic acid in the structural unit derived from the unsaturated carboxylic acid ester, for example, acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like No.
Examples of the alkyl moiety in the structural unit derived from the unsaturated carboxylic acid alkyl ester include an alkyl group having 1 to 12 carbon atoms, and specifically, methyl, ethyl, n-propyl, isopropyl, n- Examples include alkyl groups such as butyl, isobutyl, secondary butyl, 2-ethylhexyl, and isooctyl. Among them, an alkyl group having 1 to 8 carbon atoms is preferable.

  As the ethylene / unsaturated carboxylic acid ester copolymer, an ethylene / (meth) acrylic acid ester copolymer is particularly preferred. Among them, a copolymer containing a structural unit derived from one type of compound as the (meth) acrylate is preferable. Examples of the ethylene / unsaturated carboxylic acid ester copolymer include an ethylene / methyl acrylate copolymer, an ethylene / ethyl acrylate copolymer, an ethylene / n-butyl acrylate copolymer, and an ethylene / isobutyl acrylate copolymer. Examples thereof include a polymer, an ethylene / methyl methacrylate copolymer, an ethylene / ethyl methacrylate copolymer, an ethylene / n-butyl methacrylate copolymer, and an ethylene / isobutyl methacrylate copolymer.

  The content of the structural unit derived from ethylene is preferably from 40% by mass to 80% by mass, and more preferably from 50% by mass to 70% by mass based on the total mass of the ethylene / unsaturated carboxylic acid ester copolymer. Is more preferred.

The content of the structural unit derived from the unsaturated carboxylic acid ester is preferably 20% by mass to 60% by mass, and more preferably 30% by mass to 50% by mass based on the total mass of the ethylene / unsaturated carboxylic acid ester copolymer. Is more preferable.
When the content of the structural unit derived from the unsaturated carboxylic acid ester is in the above range, the haze of the intermediate film is further improved, and both the blinding property and the light transmittance can be achieved.

  The ethylene / unsaturated carboxylic acid ester copolymer may further include a structural unit derived from an unsaturated carboxylic acid ester and a monomer other than ethylene, as long as the characteristics of one embodiment of the present invention are not impaired. . However, it is preferable that the content of the structural unit derived from the other monomer does not exceed the content of the structural unit derived from the unsaturated carboxylic acid ester.

The ethylene / unsaturated carboxylic acid ester copolymer may be produced by a conventionally known method, or a commercially available product may be used.
From the viewpoint of processability and mechanical strength, the ethylene / unsaturated carboxylic acid ester copolymer has a melt flow rate (JIS-K7210 (1999)) at 190 ° C. and a load of 2160 g of 0.1 g / 10 min to 150 g / It is preferably 10 minutes, particularly preferably 0.1 g / 10 minutes to 50 g / 10 minutes.

[Ethylene / vinyl ester copolymer]
The A film contains at least one copolymer selected from the above-mentioned ethylene / unsaturated carboxylic acid ester copolymer and ethylene / vinyl ester copolymer.
The ethylene / vinyl ester copolymer contains at least a structural unit derived from ethylene and a structural unit derived from vinyl ester. The ethylene / vinyl ester copolymer may be a random copolymer, a block copolymer, or an alternating copolymer.

  Examples of the ethylene / vinyl ester copolymer include an ethylene / vinyl butyrate copolymer, an ethylene / vinyl acetate copolymer, an ethylene / vinyl propionate copolymer, and an ethylene / vinyl stearate copolymer. Vinyl acetate copolymers are preferred.

  The content of the structural unit derived from ethylene is preferably from 40% by mass to 80% by mass, and more preferably from 50% by mass to 70% by mass, based on the total mass of the ethylene / vinyl ester copolymer. .

The content of the structural unit derived from the vinyl ester is preferably from 20% by mass to 60% by mass, more preferably from 30% by mass to 50% by mass, based on the total mass of the copolymer.
When the content of the structural unit derived from the vinyl ester is within the above range, the haze of the intermediate film is further improved, and both the blinding property and the light transmittance can be achieved.

  The ethylene / vinyl ester copolymer may further contain structural units derived from monomers other than vinyl ester and ethylene, as long as the characteristics of one embodiment of the present invention are not impaired. However, it is preferable that the content of the structural unit derived from the other monomer does not exceed the content of the structural unit derived from the vinyl ester.

The ethylene / vinyl ester copolymer may be produced by a conventionally known method, or a commercially available product may be used.
From the viewpoint of processability and mechanical strength, the ethylene / vinyl ester copolymer has a melt flow rate (JIS-K7210 (1999)) at 190 ° C. and a load of 2160 g of 0.1 g / 10 min to 150 g / 10 min. It is preferable that the amount is in particular 0.1 g / 10 min to 50 g / 10 min.

The total content of the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer in the A film is as follows: the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer; 50% by mass or less, preferably 5% by mass or more and less than 45% by mass, based on the total mass of the base polymer (excluding the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer) Is more preferably 15% by mass or more and 35% by mass or less, and most preferably 20% by mass or more and 30% by mass or less.
When the total content of the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer is within the above range, the light transmittance and the blindness are excellent.

[Ethylene polymer]
The A film contains an ethylene-based polymer (however, excluding the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer).
The ethylene-based polymer may be a homopolymer obtained by polymerizing only hydrocarbons such as ethylene, propylene, and butene, and includes a structural unit derived from ethylene, and further includes another structural unit (hereinafter, also referred to as a structural unit derived from a comonomer). ) May be used. When the ethylene-based polymer is a copolymer, it may be a random copolymer, a block copolymer, or an alternating copolymer.

Examples where the ethylene-based polymer is a homopolymer include high-density polyethylene (HDPE), polypropylene, and polybutene.
Examples of the case where the ethylene-based polymer is a copolymer include an ethylene / unsaturated carboxylic acid copolymer, an ionomer of the ethylene / unsaturated carboxylic acid copolymer, and an ethylene / α-olefin copolymer.
Among ethylene-based polymers, high-density polyethylene, and ionomers of ethylene-unsaturated carboxylic acid copolymer and ethylene-unsaturated carboxylic acid copolymer are preferred, and ethylene-unsaturated carboxylic acid copolymer and ethylene-unsaturated Ionomers of carboxylic acid copolymers are more preferred.

  When the ethylene-based polymer is a copolymer, examples of the structural unit derived from a comonomer include propylene, butene, and a structural unit derived from an α-olefin such as octene, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride. Examples thereof include structural units derived from acids and unsaturated carboxylic acids such as maleic anhydride monoester. Above all, a structural unit derived from (meth) acrylic acid is preferable, and a structural unit derived from methacrylic acid is more preferable.

  When the ethylene-based polymer is a copolymer, the content of the structural unit derived from ethylene is preferably 75% by mass to 99% by mass, and preferably 80% by mass to 99% by mass based on the total mass of the ethylene-based polymer. More preferably, the content is 90% by mass to 99% by mass.

When the ethylene-based polymer is a copolymer, the content of the structural unit derived from the comonomer is preferably 1% by mass to 25% by mass, and more preferably 1% by mass to 20% by mass based on the total mass of the ethylene-based polymer. More preferably, the content is 1% by mass to 10% by mass.
When the content of the constituent unit derived from the comonomer is within the above range, the water resistance and heat resistance of the ethylene-based polymer can be further improved, and both the blinding property and the light transmittance can be achieved.

  When the ethylene-based polymer is an ethylene-unsaturated carboxylic acid copolymer, the ethylene-unsaturated carboxylic acid copolymer is a total of 100% by mass of the constituent units derived from ethylene and the constituent units derived from the unsaturated carboxylic acid. On the other hand, in a range of more than 0% by mass and 30% by mass or less (preferably in a range of more than 0% by mass and 25% by mass or less), structural units derived from other copolymerizable monomers may be contained. However, it is preferable that the content of the structural unit derived from the other copolymerizable monomer does not exceed the content of the structural unit derived from the unsaturated carboxylic acid.

  Other copolymerizable monomers include unsaturated esters, for example, vinyl esters such as vinyl acetate and vinyl propionate; methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, Examples include alkyl (meth) acrylates such as methyl methacrylate and isobutyl methacrylate. It is preferable to include a structural unit derived from another copolymer monomer in the above range since the flexibility of the ethylene / unsaturated carboxylic acid copolymer is improved.

As the ethylene polymer, an ionomer of an ethylene / unsaturated carboxylic acid copolymer can be used. The ionomer is obtained by neutralizing a carboxylic acid group in an ethylene / unsaturated carboxylic acid copolymer with a metal.
Examples of the metal that neutralizes the carboxylic acid group include alkali metals such as lithium and sodium; and polyvalent metals such as calcium, magnesium, zinc and aluminum.

  The preferred range of the content of the constituent units derived from ethylene and the unsaturated carboxylic acid monomer in the ionomer is preferably derived from the content of the constituent units derived from ethylene and the comonomer in the ethylene polymer. It is the same as the content of the structural unit.

  The degree of neutralization of the ionomer is usually preferably 80% or less. When the degree of neutralization is 80% or less, an intermediate film having both light transmittance and blindness can be obtained. Generally, the degree of neutralization is more preferably 60% or less, and still more preferably 30% or less. The lower limit of the degree of neutralization is preferably 10%.

  The above-mentioned ethylene polymer can be obtained by radical copolymerization of each polymerization component under high temperature and high pressure. The ionomer of the ethylene / unsaturated carboxylic acid copolymer can be obtained by reacting the ethylene / unsaturated carboxylic acid copolymer with a metal compound.

  From the viewpoint of processability and mechanical strength, the ethylene-based polymer has a melt flow rate (MFR) (JIS-K7210 (1999)) at 190 ° C. and a load of 2160 g of 0.1 g / 10 min to 150 g / 10 min. It is preferable that the amount is in particular 0.1 g / 10 min to 50 g / 10 min.

  The content of the ethylene polymer in the A film is preferably 50% by mass or more based on the total mass of the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer, and the ethylene polymer. It is more preferably more than 95% by mass and not more than 95% by mass, further preferably not less than 65% by mass and not more than 85% by mass, most preferably not less than 70% by mass and not more than 80% by mass.

[Other resins]
The A film may contain another resin within a range that does not impair the purpose of one embodiment of the present invention.
Examples of other resins include polypropylene, polybutene, polyisoprene, and polychloroprene.

[Other additives]
The A film may contain various additives within a range that does not impair the purpose of one embodiment of the present invention. Examples of such additives include a crosslinking agent, a crosslinking aid, an ultraviolet absorber, a light stabilizer, an antioxidant, and a silane coupling agent.

As the crosslinking agent, it is preferable to use an organic peroxide having a decomposition temperature with a half-life of 1 hour, usually 90 ° C to 180 ° C, preferably 100 ° C to 150 ° C. Examples of such an organic peroxide include t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexyl carbonate, t-butyl peroxy acetate, t-butyl peroxy benzoate, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, Methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2,5-bisperoxybenzoate t-butyl hydroperoxide, p- menthane hydroperoxide, benzoyl peroxide, p- chlorobenzoyl peroxide, t- butyl peroxy isobutyrate, etc. hydroxyheptyl peroxide and di cyclohexanone peroxide.
The content of the crosslinking agent in the A film is preferably from 0.1 to 5 parts by mass, more preferably from 0.5 to 3 parts by mass, per 100 parts by mass of the ethylene-based polymer.

Examples of the crosslinking assistant include a polyunsaturated compound. Polyunsaturated compounds include polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl fumarate and diallyl maleate; polyallyl compounds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate. (Meth) acryloxy compounds; divinylbenzene and the like.
The content of the crosslinking aid in the A film is preferably 5 parts by mass or less, more preferably 0.1 parts by mass to 3 parts by mass, based on 100 parts by mass of the ethylene-based polymer.

  Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2-carboxybenzophenone and 2-hydroxy-4-n- Benzophenone-based ultraviolet absorbers such as octoxybenzophenone; 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-5-methylphenyl) benzotriazole and Benzotriazole UV absorbers such as 2- (2'-hydroxy-5-t-octylphenyl) benzotriazole; and salicylate UV absorbers such as phenyl salicylate and p-octylphenyl salicylate.

Examples of the light stabilizer include a hindered amine light stabilizer.
As hindered amine light stabilizers, for example, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2 , 6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexanoyloxy-2,2,6,6-tetramethylpiperidine, 4- (o- (Chlorobenzoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenoxyacetoxy) -2,2,6,6-tetramethylpiperidine, 1,3,8-triaza-7,7,9, 9-tetramethyl-2,4-dioxo-3-noctyl-spiro [4,5] decane, bis (2,2,6,6-tetramethyl-4-piperidyl) Bacate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tris (2,2,6,6 -Tetramethyl-4-piperidyl) benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -2-acetoxypropane-1,2,3-tri Carboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -2-hydroxypropane-1,2,3-tricarboxylate, tris (2,2,6,6-tetramethyl-4) -Piperidyl) triazine-2,4,6-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidine) phosphite, tris (2,2,6,6- Tramethyl-4-piperidyl) butane-1,2,3-tricarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) propane-1,1,2,3-tetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate.

Examples of the antioxidant include various hindered phenol-based antioxidants and phosphite-based antioxidants.
Specific examples of the hindered phenol-based antioxidant include 2,6-di-t-butyl-p-cresol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,6-di-t-butyl-4-ethylphenol, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2,2′-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], bis [3,3-bis (4-hydroxy -3-tert-butylphenyl) butylic acid] glycol ester, 4,4'-butylidenebis (6-t-butyl-m-cresol), 2,2'-ethylidenebis (4-sec -Butyl-6-t-butylphenol), 2,2′-ethylidenebis (4,6-di-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butyl) Phenyl) butane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2,6-diphenyl-4-octadecyloxyphenol, Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4′-thiobis (6-t-butyl-m-cresol), tocopherol, 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5 -Methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzylthio) ) -1,3,5-triazine and the like.
Specific examples of phosphite-based antioxidants include 3,5-di-t-butyl-4-hydroxybenzylphosphonate dimethyl ester, bis (3,5-di-t-butyl-4-hydroxybenzyl). Ethyl phosphonate, tris (2,4-di-t-butylphenyl) phosphanate and the like can be mentioned.
The content of the antioxidant, the light stabilizer, and the ultraviolet absorber in the A film is preferably 5 parts by mass or less, and 0.1 part by mass to 3 parts by mass, when the total mass of the A film is 100 parts by mass. Is more preferred.

Examples of the silane coupling agent include a silane coupling agent having a vinyl group, an amino group or an epoxy group, and a hydrolyzing group such as an alkoxy group, and a titanate-based coupling agent.
Specific examples of the silane coupling agent include vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane. Silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyl Examples include diethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane.
The content of the silane coupling agent in the A film is preferably 5 parts by mass or less, more preferably 0.02 parts by mass to 3 parts by mass, when the total mass of the A film is 100 parts by mass. When the silane coupling agent is contained in the above range, the adhesiveness between the glass sheet described below and the A film can be improved.

In addition, the A film may contain additives such as a colorant, a light diffusing agent, a flame retardant, and a metal deactivator, if necessary, in addition to the additives described above.
Examples of the coloring agent include pigments (inorganic pigments and organic pigments), dyes, and the like. These colorants can be selected from various known ones.

  As inorganic pigments, for example, titanium dioxide, zinc white, lead white, lithopone, barite, precipitated barium sulfate, calcium carbonate, gypsum, white inorganic pigments such as precipitated silica, carbon black, lamp black, titanium black, synthetic Black inorganic pigments such as iron black, gray inorganic pigments such as zinc dust, lead suboxide, and slate powder; red inorganic pigments such as cadmium red, cadmium mercury red, silver vermilion, red iron, molybdenum red, lead red, amber, iron oxide tea Yellow inorganic pigments such as cadmium yellow, zinc yellow, orca, siena, synthetic orca, graphite, and titanium yellow; green inorganic pigments such as chromium oxide green, cobalt green, and chrome green; ultramarine, navy blue, and iron Blue and cobalt blue and other inorganic pigments and metal powder inorganic pigments.

Examples of the organic pigment include permanent red 4R, para red, first yellow G, first yellow 10G, disazo yellow G, disazo yellow GR, disazo orange, pyrazolone orange, brilliant carmine 3B, and brilliant.・ Carmin 6B, Brilliant Scarlet G, Brilliant Bordeaux 10B, Bordeaux 5B, Permanent Red F5R, Permanent Carmin FB, Risor Red R, Risor Red B, Lake Red C, Lake Red D, Brilliant Fast Azo pigments such as Scarlet, Pyrazolone Red, Bon Maroon Light, Bon Maroon Medium and Fire Red; nitroso pigments such as naphthol green B; nits such as naphthol yellow S Pigments, basic dye lakes such as rhodamine B lake and rhodamine 6G lake, mordant dye lakes such as alizarin lake, vat dye pigments such as indanthrene blue, phthalocyanine blue, phthalocyanine green, fast dye Examples include phthalocyanine pigments such as Sky Blue and dioxazine pigments such as dioxazine violet.
In addition, organic fluorescent pigments, pearl pigments, and the like can be used.

  Examples of the light diffusing agent include an inorganic spherical substance and an organic spherical substance. Examples of the inorganic spherical substance include glass beads, silica beads, silicon alkoxide beads, and hollow glass beads. Examples of the organic spherical substance include plastic beads such as acrylic beads and vinylbenzene beads.

  Examples of the flame retardant include halogen-based flame retardants such as bromide, phosphorus-based flame retardants, silicone-based flame retardants, and metal hydrates such as magnesium hydroxide and aluminum hydroxide.

The metal deactivator can be selected from compounds well-known as compounds that suppress metal damage of the thermoplastic resin. Two or more metal deactivators may be used in combination. Preferred examples of the metal deactivator include a hydrazide derivative and a triazole derivative.
Examples of the hydrazide derivative include decamethylene dicarboxyl-disalicyloyl hydrazide, 2 ′, 3-bis [3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl] propionohydrazide, and bisisophthalic acid (2-phenoxypropionyl-hydrazide) is preferred.
As the triazole derivative, 3- (N-salicyloyl) amino-1,2,4-triazole is preferably exemplified.
In addition to the hydrazide derivative and the triazole derivative, 2,2′-dihydroxy-3,3′-di- (α-methylcyclohexyl) -5,5′-dimethyldiphenylmethane and tris- (2 -Methyl-4-hydroxy-5-tert-butylphenyl) butane, a mixture of 2-mercaptobenzimidazole and a phenol condensate, and the like.

≪Other layers≫
The intermediate film may have a multilayer structure in which at least the A film and another film are stacked.
When the intermediate film has a multilayer structure, the intermediate layer contains at least the A film, has a haze at a thickness of 400 μm of 50% or more and 99.5% or less, and has a total light transmittance of 50% or more and 90% or less. The material of other films laminated on the A film is not particularly limited.
As the other film, from the viewpoint of the water resistance of the intermediate film, a film containing at least one copolymer selected from an ethylene-unsaturated carboxylic acid copolymer and an ionomer of the ethylene-unsaturated carboxylic acid copolymer Is preferred.
As a more preferred embodiment of the intermediate film, two B films containing at least one copolymer selected from an ethylene / unsaturated carboxylic acid copolymer and an ionomer of the ethylene / unsaturated carboxylic acid copolymer; An embodiment having a multilayer structure in which at least three films including the A film disposed between two B films are stacked.

Examples of the ionomer of the ethylene / unsaturated carboxylic acid copolymer and the ethylene / unsaturated carboxylic acid copolymer contained in the film B include the ethylene / unsaturated carboxylic acid copolymer and the ethylene / unsaturated carboxylic acid copolymer described in the film A. The ionomer of an acid copolymer is mentioned.
Further, the B film may include the other resin and other additives.
The haze of the B film is preferably at least 40%, more preferably at least 60%, even more preferably at least 80%.

[Physical properties of interlayer film]
The intermediate film has a haze of 50% or more and 99.5% or less and a total light transmittance of 50% or more and 90% or less at a thickness of 400 µm. When the haze and the total light transmittance are in the above ranges, the haze of the laminated glass can be 50% or more and 99.5% or less, and the total light transmittance can be 50% or more and 90% or less.

When the haze at an intermediate film thickness of 400 μm is 50% or more, the laminated glass has excellent blinding properties, and when the haze is 99.5% or less, the laminated glass has excellent light transmittance.
The haze at a thickness of 400 μm of the intermediate film is preferably from 60% to 99.5%, more preferably from 80% to 99.5%, further preferably from 85% to 99.5%, and more preferably from 90% to 99%. Most preferred.

When the total light transmittance at an intermediate film thickness of 400 μm is 50% or more, the laminated glass is excellent in light transmittance, and when the total light transmittance is 90% or less, the laminated glass is excellent in blindfold.
The total light transmittance at an intermediate film thickness of 400 μm is preferably from 60% to 90%, more preferably from 70% to 90%, and most preferably from 75% to 85%.

  The haze is a value measured according to JIS-K7136: 2000, and the total light transmittance is a value measured according to JIS-K7361: 1997.

[Formation of interlayer film]
The intermediate film can be formed by a known method using a single-layer T-die extruder, a multilayer T-die extruder, a calendar molding machine, a single-layer inflation molding machine, a multilayer inflation molding machine, or the like.

For example, when the intermediate film is formed only of the A film, at least one copolymer selected from the group consisting of an ethylene / unsaturated carboxylic acid copolymer and an ethylene / vinyl ester copolymer, and an ethylene polymer If necessary, additives such as an antioxidant, a light stabilizer, an ultraviolet absorber and a silane coupling agent are added and dry blended, supplied from a hopper of a T-die extruder, and extruded into a sheet. It is obtained by doing.
When the intermediate film is formed of only the A film, the thickness of the intermediate film is preferably from 10 μm to 5000 μm, and more preferably from 50 μm to 2000 μm.

For example, when the intermediate film has a multilayer structure, the other films can be formed in the same manner as the film A, and may be bonded to the film A using a vacuum heating bonding machine or the like after the formation. . Further, the other film may be formed integrally with the film A using a multilayer extruder to form an intermediate film having a multilayer structure.
The thickness of the other films is preferably 5 μm to 1000 μm, more preferably 10 μm to 500 μm.

  When the intermediate film has a multilayer structure in which at least three films including two B films and the A film disposed between the two B films are stacked, the thickness of each B film is 10 μm to 200 μm. The thickness of the A film is preferably 40 μm to 1800 μm.

<Laminated glass>
Laminated glass, two glasses, and at least one copolymer selected from an ethylene-unsaturated carboxylic acid ester copolymer and an ethylene-vinyl ester copolymer disposed between the two glasses, An ethylene-based polymer (excluding the ethylene-unsaturated carboxylic acid ester copolymer and the ethylene-vinyl ester copolymer), and an intermediate film (an intermediate film described above) including an A film containing the same. .
The laminated glass has a haze of 50% or more and 99.5% or less, and a total light transmittance of 50% or more and 90% or less.
If the haze is less than 50%, the blinding property is poor, and if it exceeds 99.5%, the light transmittance is poor. Haze is preferably 60% or more and 99.5% or less, more preferably 80% or more and 99.5% or less, further preferably 85% or more and 99.5% or less, further preferably 90% or more and 99.5% or less, Most preferably, it is 90% or more and 99% or less.
If the total light transmittance is less than 50%, the light transmittance is poor, and if it exceeds 90%, the blindness is poor. The total light transmittance is preferably 60% or more and 90% or less, more preferably 70% or more and 90% or less, and most preferably 75% or more and 85% or less.
The haze is a value measured according to JIS-K7136: 2000, and the total light transmittance is a value measured according to JIS-K7361: 1997.
The laminated glass of one embodiment of the present invention has the above-described interlayer film, and the haze and the total light transmittance are in the above ranges, so that the laminated glass is excellent in light transmittance and blinding, and has high water resistance. Becomes

As a configuration of the laminated glass, for example, a configuration of sheet glass / intermediate film (A film single film) / sheet glass is exemplified.
Further, the intermediate film may have a B film as the outermost layer, and the configuration of the laminated glass may be, for example, sheet glass / intermediate film (B film / A film / B film) / sheet glass. May be adopted. Further, among these configurations, a configuration in which a colorant is blended in at least one layer is also exemplified.

The material of the sheet-shaped glass is not particularly limited, and soda-lime glass is suitably used, and among them, high-transmission glass (so-called white plate glass) is preferably used. The high transmission glass is a soda lime glass having a small iron content, and has a high total light transmittance. As the sheet glass, a template glass having an embossed pattern on the surface is also preferably used. Further, as the sheet-like glass, soda lime glass (so-called blue plate glass) having a high iron content, heat ray reflection glass, heat ray absorption glass, and the like can be preferably used.
The thickness of the sheet glass (or glass plate) is not particularly limited, but is usually 4 mm or less, preferably 2.5 mm or less. Although the lower limit of the thickness of the sheet glass is not limited, it is usually 0.1 mm or more, preferably 0.5 mm or more.

The production of laminated glass is performed, for example, by inserting the interlayer film for laminated glass (intermediate film having a single film of A film or a multilayer film) between two sheets of glass and thermocompression bonding under heating and pressure. be able to. The heating temperature is, for example, preferably about 100 ° C. to 250 DEG ° C., the pressure is, for ^{example, 0.1kg / cm 2 ~30kg / cm} 2 is preferably about.

  Hereinafter, one embodiment of the present invention will be described more specifically with reference to examples, but one embodiment of the present invention is not limited to the following examples as long as the gist of the embodiment is not exceeded. Unless otherwise specified, “parts” are based on mass.

  The materials used in the following Examples and Comparative Examples, the composition of each layer, the base material, and the evaluation method are as follows.

-(1) Resin-
The following resin raw materials were prepared.
1. Ethylene / vinyl acetate copolymer (EVA)
Structural unit content derived from vinyl acetate = 41% by mass
Structural unit content derived from ethylene = 59% by mass
2. Ethylene methacrylic acid copolymer (E-MAA)
Structural unit content derived from methacrylic acid = 4% by mass
Structural unit content derived from ethylene = 96% by mass
3. Zn ionomer of ethylene / methacrylic acid copolymer Structural unit content derived from methacrylic acid = 9% by mass
Structural unit content derived from ethylene = 91% by mass
Neutralization ion = Zn ion Neutralization degree = 18%
4. Polyethylene (HDPE)
HIZEX 7000F manufactured by Prime Polymer Co., Ltd.
4. MFR (190 ° C., 2160 g load) = 0.04 g / 10 minutes Ethylene-methyl acrylate copolymer (EMA)
Structural unit content derived from methyl acrylate = 20% by mass
Structural unit content derived from ethylene = 80% by mass
5. MFR (190 ° C., 2160 g load) = 8 g / 10 min. Ethylene-ethyl acrylate copolymer (EEA)
Structural unit content derived from methyl acrylate = 15% by mass
Structural unit content derived from ethylene = 85% by mass
MFR (190 ° C., 2160 g load) = 6 g / 10 min

-(2) Substrate-
The following base materials were prepared.
3.2 mm thick blue plate tempered glass (made by Asahi Glass Co., Ltd.)
-(3) B film-
The following resin film was used for the B film.
80 parts of the above ionomer, 20 parts of the above E-MAA, and a silane coupling agent (N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane: “KBM602” manufactured by Shin-Etsu Chemical Co., Ltd.) 0 And 2 parts were mixed to prepare a composition for forming a B film, and a resin film was formed using a single-layer T-die molding machine at a resin temperature of 160 ° C. so as to have a film thickness of 75 μm. .

[Example 1]
28 parts of the above-mentioned EVA and 72 parts of the above-mentioned E-MAA were mixed, and all used a 40 mmφ coat hanger die forming machine (manufactured by Nakatani Machine Co., Ltd.) equipped with a die having a die width of 40 mm. Thus, a single-layer sheet (film A) having a thickness of 250 μm was prepared.
Next, a 3.2 mm-thick blue plate reinforced glass (75 mm × 120 mm), the above-mentioned B film, the single-layer sheet (A film) having a thickness of 250 μm obtained above, the above-mentioned B film, and 3.2 mm-thick blue Plate-reinforced glass (75 mm × 120 mm) is laminated in this order, and the laminated body is subjected to a vacuum heating bonding machine (LM-50 × 50S, a double vacuum tank bonding machine manufactured by NPC) at 150 ° C. for 8 minutes. A laminated glass sample having a structure of laminated blue plate / glass (intermediate film (B film / A film / B film) / blue plate strengthened glass) was prepared.

<Evaluation>
The following various evaluations were performed using the obtained laminated glass sample. The evaluation results are shown in Table 1 below.

(Haze and total light transmittance)
Using a laminated glass sample, the total light transmittance (%) was measured according to JIS-K7361 and the haze (%) was measured according to JIS-K7136 using a haze meter (manufactured by Suga Test Instruments Co., Ltd.).

(water resistant)
The laminated glass sample was boiled in boiling water at 100 ° C. for 2 hours, the appearance of the boiled sample was visually observed, haze and total light transmittance were measured, and water resistance was evaluated according to the following criteria. The higher the degree of discoloration of the sample, the worse the water resistance was evaluated.

-Evaluation criteria-
A: There is no change in appearance, and the rate of change in haze and total light transmittance is less than 3%.
B: Appearance change, one of haze and change rate of total light transmittance is 3% or more.

[Examples 2 to 4]
In Example 1, a laminated glass sample of each example was produced in the same manner as in Example 1 except that the kind and the mixing ratio of the resin of the film A were changed as shown in Table 1 below.
Various evaluations were also performed on the laminated glass samples of the respective examples, similarly to the example 1. Table 1 shows the evaluation results.

[Comparative Example 1]
A laminated glass sample was prepared in the same manner as in Example 1 except that the resin of the intermediate film in Example 1 was changed to 100 parts of the above EVA. Various evaluations were also performed on the laminated glass sample of Comparative Example 1 in the same manner as in Example 1. Table 1 shows the evaluation results.

From Table 1, it can be seen that Examples 1 to 4 have excellent blinding properties and high water resistance.
Comparative Example 1 has a low haze and is inferior in blindness. In addition, as shown in FIG. 1, it can be seen that Comparative Example 1 is whitened and inferior in water resistance.

The disclosure of Japanese Patent Application No. 2014-210738 filed on October 15, 2014 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned herein are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.

Claims (10)

Two glasses,
At least one copolymer selected from the group consisting of an ethylene-unsaturated carboxylic acid ester copolymer and an ethylene-vinyl ester copolymer and an ethylene-based polymer (provided that the ethylene-unsaturated (Excluding a saturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer).
A laminated glass having a haze of 50% to 99.5% and a total light transmittance of 50% to 85 %.   Two B films, wherein the intermediate film contains at least one copolymer selected from an ethylene / unsaturated carboxylic acid copolymer and an ionomer of the ethylene / unsaturated carboxylic acid copolymer, and the two B films The laminated glass according to claim 1, wherein the laminated glass has a multilayer structure in which at least three films including the A film disposed therebetween are laminated.   The laminated glass according to claim 2, wherein the B film further contains a silane coupling agent.   The ethylene-unsaturated carboxylic acid ester copolymer is an ethylene- (meth) acrylate copolymer; the ethylene-vinyl ester copolymer is an ethylene-vinyl acetate copolymer; Is at least one copolymer selected from ethylene / unsaturated carboxylic acid copolymers and ionomers of ethylene / unsaturated carboxylic acid copolymers. The combination according to any one of claims 1 to 3, wherein Glass.   The ethylene / unsaturated carboxylic acid copolymer contained in the A film has a content of a structural unit derived from an unsaturated carboxylic acid of 1% by mass to 10% by mass based on the total mass of the copolymer. Item 5. A laminated glass according to item 4.   The total content of the ethylene / unsaturated carboxylic acid ester copolymer and the ethylene / vinyl ester copolymer is the ethylene / unsaturated carboxylic acid ester copolymer, the ethylene / vinyl ester copolymer, and the ethylene 5% by mass or more and less than 45% by mass with respect to the total mass of the system-based polymer, wherein the content of the ethylene-based polymer is the ethylene-unsaturated carboxylic acid ester copolymer or the ethylene-vinyl ester copolymer The laminated glass according to any one of claims 1 to 5, wherein the amount is more than 55% by mass and 95% by mass or less based on the total mass of the ethylene-based polymer. In the ethylene / unsaturated carboxylic acid ester copolymer, the content of the structural unit derived from the unsaturated carboxylic acid ester is from 20% by mass to 60% by mass relative to the total mass of the ethylene / unsaturated carboxylic acid ester copolymer. The laminated glass according to any one of claims 1 to 6, which is a mass%. The content of the structural unit derived from a vinyl ester in the ethylene / vinyl ester copolymer is 20% by mass to 60% by mass based on the total mass of the ethylene / vinyl ester copolymer. Item 10. The laminated glass according to any one of items 7 to 9. When the ethylene-based polymer is a copolymer, the content of structural units derived from a comonomer is 1% by mass to 25% by mass based on the total mass of the ethylene-based polymer. The laminated glass according to any one of the above. At least one copolymer selected from an ethylene / unsaturated carboxylic acid ester copolymer and an ethylene / vinyl ester copolymer; and an ethylene polymer (provided that the ethylene / unsaturated carboxylic acid ester copolymer and the wherein the excluding ethylene-vinyl ester copolymer), an a film containing, Ruhe size put in thickness 400μm is less than 99.5% 50%, the total light transmittance in the thickness 400μm 50% or more An interlayer film for laminated glass of 85 % or less.