Intermediate film for laminated glass, roll, and laminated glass
阅读说明：本技术 夹层玻璃用中间膜、卷体和夹层玻璃 (Intermediate film for laminated glass, roll, and laminated glass ) 是由 冲塚真珠美 石川由贵 河田晋治 于 2019-01-30 设计创作，主要内容包括：本发明提供能够在透明性得到了提高的中间膜中提高隔音性和层间粘接力的夹层玻璃用中间膜。本发明的夹层玻璃用中间膜为具有1层或2层以上结构的夹层玻璃用中间膜,所述中间膜具备包含乙烯基单体聚合物的第1层,所述乙烯基单体聚合物为包含单体的聚合性组合物的聚合物,所述单体含有具有氢键合性的官能团,将所述夹层玻璃用中间膜配置在2片基于JIS R3202并且厚度2.0mm、长度30mm且宽度2.5cm的浮法玻璃之间而得的夹层玻璃基于JIS K6714并使用雾度计测定的雾度为0.5％以下。(The present invention provides an interlayer film for a laminated glass, which can improve sound insulation and interlayer adhesion in the interlayer film with improved transparency. The interlayer film for laminated glass of the present invention is an interlayer film for laminated glass having a structure of 1 layer or 2 or more layers, the interlayer film comprising a1 st layer comprising a vinyl monomer polymer, the vinyl monomer polymer being a polymer of a polymerizable composition comprising a monomer having a functional group having hydrogen bonding properties, and the interlayer film for laminated glass having a haze of 0.5% or less as measured by a haze meter based on JIS K6714, the laminated glass being obtained by disposing 2 pieces of float glass having a thickness of 2.0mm, a length of 30mm and a width of 2.5cm based on JIS R3202.)
1. An interlayer film for laminated glass having a structure of 1 or 2 or more layers, wherein,
the intermediate film has a1 st layer containing a vinyl monomer polymer,
the vinyl monomer polymer is a polymer of a polymerizable composition containing a monomer having a functional group having hydrogen bonding properties,
the laminated glass obtained through the following steps 1,2 and 3 has a haze of 0.5% or less as measured by a haze meter in accordance with JIS K6714,
step 1: preparing an interlayer film having a length of 30mm and a width of 2.5cm, preparing 2 sheets of transparent float glass having a thickness of 2.0mm, a length of 30mm and a width of 2.5cm based on JIS R3202, and sandwiching the interlayer film between the 2 sheets of transparent float glass to obtain a laminate,
and a2 nd step: the obtained laminate was put into a rubber bag, degassed under a vacuum of 2.6kPa for 20 minutes, moved into an oven in a degassed state, further held at 90 ℃ for 30 minutes and vacuum-pressed to pre-press the laminate,
and a 3 rd step: the laminated body was preliminarily laminated in an autoclave at 135 ℃ and 1.2MPa for 20 minutes to obtain a laminated glass.
2. The interlayer film for laminated glass according to claim 1, wherein,
the 1 st layer comprises polyvinyl acetate as the vinyl monomer polymer,
the polyvinyl acetate is a polymer of a polymerizable composition containing vinyl acetate and a monomer containing the functional group having hydrogen bonding properties.
3. The interlayer film for laminated glass according to claim 1, wherein,
the 1 st layer contains a (meth) acrylic polymer as the vinyl monomer polymer,
the (meth) acrylic polymer is a polymer of a polymerizable composition containing the following monomers:
a (meth) acrylic monomer having no hydrogen-bonding functional group in a side chain, and
a monomer containing the functional group having hydrogen bonding property.
4. The interlayer film for laminated glass according to claim 2, wherein,
the polyvinyl acetate contains a structural unit derived from the monomer having the hydrogen-bonding functional group at a ratio of 0.2 mol% to 30 mol%.
5. The interlayer film for laminated glass according to claim 3,
the (meth) acrylic polymer contains a structural unit derived from the monomer having the hydrogen-bonding functional group at a ratio of 0.2 mol% to 45 mol%.
6. The interlayer film for laminated glass according to claim 2 or 4,
the weight average molecular weight of the polyvinyl acetate is more than 30 ten thousand.
7. The interlayer film for laminated glass according to claim 3 or 5,
the weight average molecular weight of the (meth) acrylic polymer is 30 ten thousand or more.
8. The interlayer film for laminated glass according to any one of claims 1 to 7,
the functional group in the monomer having a hydrogen-bonding functional group is a hydroxyl group.
9. The interlayer film for laminated glass according to any one of claims 1 to 8,
the intermediate film is provided with a2 nd layer,
the 2 nd layer is laminated on the 1 st surface of the 1 st layer.
10. The interlayer film for laminated glass according to claim 9, wherein,
the 2 nd layer comprises a thermoplastic resin.
11. The interlayer film for laminated glass according to claim 10,
the thermoplastic resin in the 2 nd layer is a polyvinyl acetal resin.
12. The interlayer film for laminated glass according to any one of claims 9 to 11,
the intermediate film is provided with a 3 rd layer,
the 3 rd laminated layer is on a2 nd surface of the 1 st layer opposite the 1 st surface.
13. The interlayer film for laminated glass according to claim 12, wherein,
the 3 rd layer comprises a thermoplastic resin.
14. The interlayer film for laminated glass according to claim 13, wherein,
the thermoplastic resin in the 3 rd layer is a polyvinyl acetal resin.
15. The interlayer film for laminated glass according to any one of claims 12 to 14,
the 1 st layer contains a plasticizer and, optionally,
the 2 nd layer contains a plasticizer and, optionally,
the 3 rd layer comprises a plasticizer.
16. The interlayer film for laminated glass according to claim 15, wherein,
the 2 nd layer comprises a thermoplastic resin,
the 3 rd layer comprises a thermoplastic resin,
the content of the plasticizer in the 1 st layer with respect to 100 parts by weight of the vinyl monomer polymer is higher than the content of the plasticizer in the 2 nd layer with respect to 100 parts by weight of the thermoplastic resin,
the content of the plasticizer in the 1 st layer with respect to 100 parts by weight of the vinyl monomer polymer is higher than the content of the plasticizer in the 3 rd layer with respect to 100 parts by weight of the thermoplastic resin.
17. A roll body, comprising:
a winding core, and
the interlayer film for laminated glass according to any one of claims 1 to 16, wherein,
the interlayer film for laminated glass is wound around the outer periphery of the winding core.
18. A laminated glass is provided with:
the 1 st laminated glass member,
The 2 nd laminated glass member, and
the interlayer film for laminated glass according to any one of claims 1 to 16, wherein,
the interlayer film for laminated glass is disposed between the 1 st laminated glass member and the 2 nd laminated glass member.
19. A laminated glass is provided with:
the 1 st laminated glass member,
The 2 nd laminated glass member, and
an interlayer film for laminated glass disposed between the 1 st laminated glass member and the 2 nd laminated glass member,
the intermediate film has a1 st layer containing a vinyl monomer polymer,
the vinyl monomer polymer is a polymer of a polymerizable composition comprising the following monomers:
vinyl acetate or (meth) acrylic monomer, and
a monomer having a functional group having hydrogen bonding property, and
the laminated glass has a haze of 0.5% or less, as measured by a haze meter according to JIS K6714.
Technical Field
The present invention relates to an interlayer film for laminated glass for obtaining a laminated glass. The present invention also relates to a roll using the interlayer film for laminated glass, and a laminated glass.
Background
The laminated glass is less in scattering of broken glass pieces and excellent in safety even when broken by external impact. Therefore, the laminated glass is widely used in vehicles, railway vehicles, spacecrafts, ships, buildings, and the like. The laminated glass is produced by sandwiching an interlayer film for laminated glass between two glass plates.
As an example of the interlayer film for a laminated glass,
Disclosure of Invention
Technical problem to be solved by the invention
In the conventional interlayer film described in
In addition, in the conventional interlayer film described in
In addition, in the case where the transparency of the interlayer film is improved in the conventional interlayer film, it is sometimes difficult to improve the sound insulating property and the interlayer adhesion.
The present invention aims to provide an interlayer film for laminated glass, which has improved transparency, and which can improve sound insulation properties and interlayer adhesion. Another object of the present invention is to provide a roll using the interlayer film for laminated glass, and a laminated glass.
Means for solving the problems
According to a broad aspect of the present invention, there is provided an interlayer film for laminated glass (hereinafter, may be referred to as an interlayer film) having a structure of 1 or 2 or more layers, the interlayer film comprising a1 st layer comprising a vinyl monomer polymer which is a polymer of a polymerizable composition comprising a monomer having a functional group having hydrogen bonding properties, wherein the laminated glass obtained through the following 1 st, 2 nd and 3 rd steps has a haze of 0.5% or less as measured by a haze meter based on JIS K6714.
Step 1: an interlayer film having a length of 30mm and a width of 2.5cm was prepared, 2 sheets of transparent float glass having a thickness of 2.0mm, a length of 30mm and a width of 2.5cm were prepared according to JIS R3202, and the interlayer film was sandwiched between the 2 sheets of transparent float glass, thereby obtaining a laminate.
And a2 nd step: the obtained laminate was placed in a rubber bag, degassed under a vacuum of 2.6kPa for 20 minutes, moved to an oven in a degassed state, and further held at 90 ℃ for 30 minutes to be vacuum-pressed, thereby pre-pressing the laminate.
And a 3 rd step: the laminated body was preliminarily laminated in an autoclave at 135 ℃ and 1.2MPa for 20 minutes to obtain a laminated glass.
In a specific aspect of the intermediate film of the present invention, the 1 st layer contains polyvinyl acetate as the vinyl monomer polymer, and the polyvinyl acetate is a polymer of a polymerizable composition containing vinyl acetate and a monomer containing the functional group having hydrogen bonding property.
In one specific embodiment of the intermediate film of the present invention, the 1 st layer contains a (meth) acrylic polymer as the vinyl monomer polymer, and the (meth) acrylic polymer is a polymer of a polymerizable composition containing: a (meth) acrylic monomer having no hydrogen-bonding functional group in a side chain thereof, and a monomer having the hydrogen-bonding functional group.
In one specific embodiment of the intermediate film of the present invention, the polyvinyl acetate contains a structural unit derived from the monomer having the hydrogen-bonding functional group at a ratio of 0.2 mol% to 30 mol%.
In one specific embodiment of the intermediate film of the present invention, the (meth) acrylic polymer contains a structural unit derived from the monomer having the hydrogen-bonding functional group at a ratio of 0.2 mol% to 45 mol%.
In one specific embodiment of the intermediate film of the present invention, the polyvinyl acetate has a weight average molecular weight of 30 ten thousand or more.
In one specific embodiment of the intermediate film of the present invention, the weight average molecular weight of the (meth) acrylic polymer is 30 ten thousand or more.
In one specific embodiment of the intermediate film of the present invention, the functional group in the monomer having a hydrogen-bonding functional group is a hydroxyl group.
In one specific aspect of the intermediate film of the present invention, the intermediate film includes a2 nd layer, and the 2 nd layer is laminated on a1 st surface of the 1 st layer.
In a specific aspect of the intermediate film of the present invention, the 2 nd layer contains a thermoplastic resin.
In one specific aspect of the intermediate film of the present invention, the thermoplastic resin in the 2 nd layer is a polyvinyl acetal resin.
In one specific aspect of the intermediate film of the present invention, the intermediate film includes a 3 rd layer, and the 3 rd layer is laminated on a2 nd surface of the 1 st layer opposite to the 1 st surface.
In a specific aspect of the intermediate film of the present invention, the 3 rd layer contains a thermoplastic resin.
In one specific aspect of the intermediate film of the present invention, the thermoplastic resin in the 3 rd layer is a polyvinyl acetal resin.
In a specific embodiment of the intermediate film of the present invention, the 1 st layer contains a plasticizer, the 2 nd layer contains a plasticizer, and the 3 rd layer contains a plasticizer.
In a specific aspect of the intermediate film of the present invention, the 2 nd layer contains a thermoplastic resin, the 3 rd layer contains a thermoplastic resin, the content of the plasticizer in the 1 st layer with respect to 100 parts by weight of the vinyl monomer polymer is higher than the content of the plasticizer in the 2 nd layer with respect to 100 parts by weight of the thermoplastic resin, and the content of the plasticizer in the 1 st layer with respect to 100 parts by weight of the vinyl monomer polymer is higher than the content of the plasticizer in the 3 rd layer with respect to 100 parts by weight of the thermoplastic resin.
According to a broad aspect of the present invention, there is provided a roll body including a roll core and the interlayer film for laminated glass, the interlayer film for laminated glass being wound around an outer periphery of the roll core.
According to a broad aspect of the present invention, there is provided a laminated glass comprising a1 st laminated glass member, a2 nd laminated glass member, and the interlayer film for laminated glass, wherein the interlayer film for laminated glass is disposed between the 1 st laminated glass member and the 2 nd laminated glass member.
According to a broad aspect of the present invention, there is provided a laminated glass comprising a1 st laminated glass member, a2 nd laminated glass member, and an interlayer film for laminated glass disposed between the 1 st laminated glass member and the 2 nd laminated glass member, wherein the interlayer film comprises a1 st layer comprising a vinyl monomer polymer, the vinyl monomer polymer being a polymer of a polymerizable composition comprising: vinyl acetate or (meth) acrylic acid monomer, and a monomer having a functional group having hydrogen bonding properties, wherein the laminated glass has a haze of 0.5% or less as measured by a haze meter according to JIS K6714.
ADVANTAGEOUS EFFECTS OF INVENTION
The interlayer film for laminated glass of the present invention has a structure having 1 or 2 or more layers. The interlayer film for laminated glass of the present invention comprises a1 st layer comprising a vinyl monomer polymer. In the interlayer film for laminated glass of the present invention, the vinyl monomer polymer is a polymer of a polymerizable composition containing a monomer having a hydrogen-bonding functional group. In the interlayer film for laminated glass of the present invention, the laminated glass obtained through the above-described
The laminated glass of the present invention comprises a1 st laminated glass member, a2 nd laminated glass member, and an interlayer film for laminated glass disposed between the 1 st laminated glass member and the 2 nd laminated glass member. In the laminated glass of the present invention, the interlayer film includes the
The present invention will be described in detail below.
(intermediate film for laminated glass)
The interlayer film for laminated glass of the present invention (hereinafter, may be referred to as an interlayer film) has a structure of 1 layer or 2 or more layers.
The intermediate film of the present invention has a
In the case of the interlayer film of the present invention, the laminated glass obtained through the following
Step 1: an interlayer film having a length of 30mm and a width of 2.5cm was prepared, 2 sheets of transparent float glass having a thickness of 2.0mm, a length of 30mm and a width of 2.5cm were prepared according to JIS R3202, and the interlayer film was sandwiched between the 2 sheets of transparent float glass, thereby obtaining a laminate.
And a2 nd step: the obtained laminate was placed in a rubber bag, degassed under a vacuum of 2.6kPa for 20 minutes, moved to an oven in a degassed state, and further held at 90 ℃ for 30 minutes to be vacuum-pressed, thereby pre-pressing the laminate.
And a 3 rd step: the laminated body was preliminarily laminated in an autoclave at 135 ℃ and 1.2MPa for 20 minutes to obtain a laminated glass.
In the present invention, since the interlayer film has the above-described configuration, the sound insulating property and the interlayer adhesion can be improved in the interlayer film having improved transparency. In the present invention, for example, the adhesion of the 1 st layer to the 2 nd layer can be improved. For example, even if the intermediate film is bent or rolled, peeling is less likely to occur.
In the present invention, the adhesion of the 1 st layer to the laminated glass member and the adhesion of the 1 st layer to other layers in the interlayer film can be improved. In particular, the adhesion of the 1 st layer to the other layers in the interlayer film can be improved. In particular, when the other layer contains a polyvinyl acetal resin, the adhesion of the 1 st layer to the other layer containing a polyvinyl acetal resin can be improved.
The intermediate film of the present invention may have a 1-layer structure of only the 1 st layer. The intermediate film of the present invention may have a 2-layer structure, a 2-layer or more structure, a 3-layer structure, or a 3-layer or more structure. The intermediate film may be a single layer intermediate film or a multilayer intermediate film.
The interlayer film of the present invention may include a1 st layer and a2 nd layer laminated on the 1 st surface of the 1 st layer, from the viewpoint of effectively improving the sound insulation property and the adhesiveness between the layers.
The interlayer film of the present invention may include a1 st layer and a2 nd layer laminated on a1 st surface of the 1 st layer, and may further include a 3 rd layer laminated on a2 nd surface of the 1 st layer opposite to the 1 st surface, from the viewpoint of effectively improving the sound insulation property and the adhesiveness between the layers. In this case, the 1 st layer contains the vinyl monomer polymer. In the present invention, the adhesion of the 1 st layer to the 2 nd layer can be improved, and the adhesion of the 1 st layer to the 3 rd layer can be improved.
From the viewpoint of effectively improving the sound-insulating property and the adhesiveness between the layers, the interlayer film of the present invention may further include a 4 th layer disposed on the 2 nd layer opposite to the 1 st layer side, and may further include a 5 th layer disposed on the 3 rd layer opposite to the 1 st layer side. The 4 th layer may be laminated on a surface of the 2 nd layer opposite to the 1 st layer side. The 5 th layer may be laminated on a surface of the 3 rd layer opposite to the 1 st layer side.
From the viewpoint of effectively improving the sound-insulating property and the adhesion between the interlayer and the glass, the 1 st layer is preferably not a surface layer in the interlayer, and is preferably an interlayer in the interlayer. However, the 1 st layer may be a surface layer in an intermediate film. The 2 nd layer, the 3 rd layer, the 4 th layer and the 5 th layer may be a surface layer in an intermediate film or an intermediate layer in an intermediate film, respectively.
In the case of the interlayer film, the laminated glass obtained through the
The interlayer film preferably has a visible light transmittance of 70% or more, more preferably 80% or more, and still more preferably 85% or more, from the viewpoint of improving the transparency of the laminated glass.
The visible light transmittance was measured by using a spectrophotometer (HITACHI HIGH-TECH, "U-4100") in accordance with JIS R3211: 1998, the measurement is carried out at a wavelength of 380 to 780 nm.
The visible light transmittance of the interlayer film was measured by disposing an interlayer film between 2 sheets of transparent glass. The thickness of the transparent glass is preferably 2.0 mm.
Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.
Fig. 1 is a cross-sectional view schematically showing an interlayer film for laminated glass according to
The
Fig. 5 is a perspective view schematically showing a roll body obtained by winding the interlayer film for laminated glass shown in fig. 1.
The
The roll 51 shown in fig. 5 includes a winding core 61 and an
Fig. 2 is a cross-sectional view schematically showing an interlayer film for laminated glass according to
The interlayer film 11A shown in fig. 2 is a single-layer interlayer film having a 1-layer structure. The interlayer film 11A is the 1 st layer. The interlayer film 11A is used to obtain a laminated glass. The interlayer film 11A is an interlayer film for laminated glass.
The intermediate film, the 1 st layer, the 2 nd layer and the 3 rd layer of the present invention, and the components used in the intermediate film will be described in detail below.
(resin)
The 1 st layer contains a vinyl monomer polymer (hereinafter, sometimes referred to as vinyl monomer polymer (1)). The vinyl monomer polymer (1) in the
The 1 st layer preferably contains polyvinyl acetate (hereinafter, sometimes referred to as polyvinyl acetate (1)) as the vinyl monomer polymer. The polyvinyl acetate (1) in the
The polyvinyl acetate (1) is a polymer of a polymerizable composition containing vinyl acetate and a monomer a containing a functional group a1 having hydrogen bonding properties.
The polyvinyl acetate (1) has: structural units derived from vinyl acetate, and structural units derived from monomer a.
The functional group a1 having hydrogen bonding property is a hydroxyl group, an amide group, an amino group, a carboxyl group or an ether group. The hydroxyl group may be a phenolic hydroxyl group. From the viewpoint of effectively improving sound-insulating properties and interlayer adhesion (adhesion between the 1 st layer and another layer, and adhesion between the 1 st layer and a laminated glass member), the functional group a1 is preferably a hydroxyl group, an amide group, or an ether group, and more preferably a hydroxyl group. In this case, for example, the hydroxyl group contained in another layer or a laminated glass member forms a hydrogen bond with the functional group a1, whereby the interlayer adhesion can be effectively improved.
Examples of the monomer A include the following monomers. Examples of the monomer having a hydroxyl group include: 3-methyl-3-buten-1-ol, ethylene glycol monovinyl ether, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol monovinyl ether, and the like. Examples of the monomer having an amide group include N, N-dimethylaminopropyl (meth) acrylamide, N-dimethyl (meth) acrylamide, (meth) acryloylmorpholine, N-isopropyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide and the like. Examples of the monomer having an amino group include N-dialkylaminoalkyl (meth) acrylamide and N, N-dialkylaminoalkyl (meth) acrylamide. Examples of the monomer having a carboxyl group include 2-acryloyloxyethyl succinate and (meth) acrylic acid. Examples of the monomer having an ether group include (meth) acrylic acid esters: glycidyl (meth) acrylate; 3-propyloxetan-3-yl methyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, (3-butyloxetan-3-yl) methyl (meth) acrylate, (3-ethyloxetan-3-yl) ethyl (meth) acrylate, (3-ethyloxetan-3-yl) propyl (meth) acrylate, (3-ethyloxetan-3-yl) butyl (meth) acrylate, (3-ethyloxetan-3-yl) pentyl (meth) acrylate, (3-ethyloxetan-3-yl) hexyl (meth) acrylate, (2 (meth) acrylate, 2-dimethyl-1, 3-dioxolan-4-yl) methyl ester, (meth) acrylic acid (2-methyl-2-ethyl-1, 3-dioxolan-4-yl) methyl ester, (meth) acrylic acid (2-methyl-2-isobutyl-1, 3-dioxolan-4-yl) methyl ester, (meth) acrylic acid (2-cyclohexyl-1, 3-dioxolan-4-yl) methyl ester, cyclic trimethylolpropane formal acrylate, (meth) acryloyl morpholine, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and the like.
From the viewpoint of effectively improving the sound-insulating property, the weight average molecular weight of the polyvinyl acetate (1) is preferably 25 ten thousand or more, more preferably 30 ten thousand or more, further preferably 40 ten thousand or more, and particularly preferably 50 ten thousand or more. From the viewpoint of effectively improving the interlayer adhesion, the weight average molecular weight of the polyvinyl acetate (1) is preferably 200 ten thousand or less, more preferably 170 ten thousand or less, further preferably 120 ten thousand or less, and particularly preferably 90 ten thousand or less.
The weight average molecular weight means a weight average molecular weight in polystyrene measured by Gel Permeation Chromatography (GPC).
The method for synthesizing the polyvinyl acetate (1) by polymerizing the polymerizable composition is not particularly limited. Examples of the synthesis method include solution polymerization, suspension polymerization, and UV polymerization. The method for producing the polyvinyl acetate (1) may be a solution polymerization method or a suspension polymerization method. The method for producing the polyvinyl acetate (1) may be a solution polymerization method, a method other than the solution polymerization method, or a suspension polymerization method.
The method for synthesizing polyvinyl acetate (1) is preferably a solution polymerization method from the viewpoint of improving the transparency of the interlayer film and effectively improving the sound insulation property and the interlayer adhesion in the interlayer film having improved transparency. When the method for synthesizing the polyvinyl acetate (1) is a suspension polymerization method, the haze of a laminated glass having an interlayer tends to be increased. When the method for synthesizing polyvinyl acetate (1) is a solution polymerization method, the haze of a laminated glass having an interlayer film is greatly reduced.
However, even if the method for synthesizing the polyvinyl acetate (1) is a suspension polymerization method, the haze of the laminated glass provided with the interlayer film can be reduced by appropriately selecting the surfactant and the dispersant. The dispersant used when the polyvinyl acetate (1) is synthesized by a suspension polymerization method is preferably a polymer dispersant or a reactive surfactant from the viewpoint of adhesiveness. When the dispersant is a polymer dispersant, the dispersant can be prevented from easily migrating to another layer when an interlayer film is laminated, and the interlayer adhesion can be prevented from being reduced due to the diffusion of the dispersant to the layer interface or the glass interface. Examples of the polymer dispersant include a block copolymer of ethylene oxide and propylene oxide. Examples of the reactive surfactant include polymerizable compounds described later.
From the viewpoint of effectively improving the sound-insulating property and the interlayer adhesion, the proportion of the structural unit derived from the monomer a in 100 mol% of the total structural units of the polyvinyl acetate (1) is preferably 0.1 mol% or more, more preferably 0.2 mol% or more, still more preferably 0.4 mol% or more, and particularly preferably 0.5 mol% or more. From the viewpoint of effectively improving the sound-insulating property and the interlayer adhesion, the proportion of the structural unit derived from the monomer a in 100 mol% of the total structural units of the polyvinyl acetate (1) is preferably 40 mol% or less, and more preferably 30 mol% or less. Polyvinyl acetate (1) preferably contains structural units derived from monomer A in this preferred ratio. When the proportion of the structural unit derived from the monomer a is not more than the upper limit, intermolecular hydrogen bonding of polyvinyl acetate derived from the monomer a can be suppressed, and the interlayer adhesive strength can be suppressed from decreasing.
The polyvinyl acetate (1) includes a copolymer of vinyl acetate and the monomer a, and a polymerizable compound (copolymerization component) other than these compounds. The polymerizable composition may contain vinyl acetate and a polymerizable compound other than the monomer a. In the polymerizable composition, vinyl acetate is preferably contained as a main component as the polymerizable compound. The proportion of the structural unit (skeleton) derived from vinyl acetate in 100 mol% of the total structural units (skeletons) of the polyvinyl acetate (1) is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 90 mol% or more. Examples of the polymerizable compound other than vinyl acetate include a (meth) acrylic compound, a styrene compound, and an isoprene compound.
Examples of the polymerizable compound other than vinyl acetate include benzyl acrylate, styrene, vinyl benzoate, allyl benzoate, phenylphenol ethoxy acrylate, pentabromophenyl acrylate, and pentabromobenzyl acrylate. By using these polymerizable compounds, when the
Examples of the polymerizable compound other than vinyl acetate include polyoxyethylene styrenated propenyl phenyl ether sulfate ammonium, polyoxyethylene nonylphenyl phenyl ether sulfate ammonium, polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium, polyoxyethylene styrenated propenyl phenyl ether and polyoxyethylene-1- (allyloxymethyl) alkyl ether. When these polymerizable compounds are used as the reactive surfactant, an intermediate film having high transparency can be obtained even in the case of the suspension polymerization method.
The 1 st layer preferably contains a (meth) acrylic polymer (hereinafter, sometimes referred to as (meth) acrylic polymer (1)) as the vinyl monomer polymer. The (meth) acrylic polymer (1) in the
The (meth) acrylic polymer (1) is a polymer of a polymerizable composition comprising a (meth) acrylic monomer having no hydrogen-bonding functional group in the side chain and a monomer A having a hydrogen-bonding functional group A1.
The (meth) acrylic polymer (1) has: the side chain does not contain a structural unit derived from a (meth) acrylic monomer and a structural unit derived from a monomer a, the structural unit having a hydrogen bonding functional group.
The functional group a1 having hydrogen bonding property is a hydroxyl group, an amide group, an amino group, a carboxyl group or an ether group. The hydroxyl group may be a phenolic hydroxyl group. The functional group a1 is preferably a hydroxyl group or an amide group, and more preferably a hydroxyl group, from the viewpoint of effectively improving sound-insulating properties and interlayer adhesion (adhesion between the 1 st layer and another layer, and adhesion between the 1 st layer and a laminated glass member). In this case, for example, the hydroxyl group contained in another layer or a laminated glass member can form a hydrogen bond with the functional group a1, whereby the interlayer adhesion can be effectively improved.
Examples of the monomer A include the following monomers. Examples of the monomer having a hydroxyl group include 3-methyl-3-buten-1-ol, ethylene glycol monovinyl ether, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, and diethylene glycol monovinyl ether. Examples of the monomer having an amide group include N, N-dimethylaminopropyl (meth) acrylamide, N-dimethyl (meth) acrylamide, (meth) acryloylmorpholine, N-isopropyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide and the like. Examples of the monomer having an amino group include N-dialkylaminoalkyl (meth) acrylamide and N, N-dialkylaminoalkyl (meth) acrylamide. Examples of the monomer having a carboxyl group include 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalate, and (meth) acrylic acid. Examples of the monomer having an ether group include (meth) acrylic acid esters: glycidyl (meth) acrylate; 3-propyloxetan-3-yl methyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, (3-butyloxetan-3-yl) methyl (meth) acrylate, (3-ethyloxetan-3-yl) ethyl (meth) acrylate, (3-ethyloxetan-3-yl) propyl (meth) acrylate, (3-ethyloxetan-3-yl) butyl (meth) acrylate, (3-ethyloxetan-3-yl) pentyl (meth) acrylate, (3-ethyloxetan-3-yl) hexyl (meth) acrylate; gamma-butyrolactone (meth) acrylate, (2, 2-dimethyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, (2-methyl-2-ethyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, (2-methyl-2-isobutyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, (2-cyclohexyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal acrylate, (meth) acryloylmorpholine, methoxypolyethylene glycol (meth) acrylate, and phenoxypolyethylene glycol (meth) acrylate, and the like.
From the viewpoint of further effectively improving the sound-insulating property, the monomer having an ether group is preferably a (meth) acrylate having a cyclic ether structure. Examples of the (meth) acrylate having a cyclic ether structure include: glycidyl (meth) acrylate; 3-propyloxetan-3-yl methyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, (3-butyloxetan-3-yl) methyl (meth) acrylate, (3-ethyloxetan-3-yl) ethyl (meth) acrylate, (3-ethyloxetan-3-yl) propyl (meth) acrylate, (3-ethyloxetan-3-yl) butyl (meth) acrylate, (3-ethyloxetan-3-yl) pentyl (meth) acrylate, (3-ethyloxetan-3-yl) hexyl (meth) acrylate; gamma-butyrolactone (meth) acrylate, (2, 2-dimethyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, (2-methyl-2-ethyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, (2-methyl-2-isobutyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, (2-cyclohexyl-1, 3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal acrylate, and (meth) acryloylmorpholine, and the like.
From the viewpoint of further effectively improving the sound-insulating property, the (meth) acrylate having a cyclic ether structure is preferably cyclic trimethylolpropane formal acrylate.
From the viewpoint of further effectively improving the sound-insulating property, the (meth) acrylic monomer preferably contains a (meth) acrylate having an aromatic ring. The (meth) acrylate having an aromatic ring may be the (meth) acrylic monomer or the monomer a having no hydrogen-bonding functional group in the side chain.
Examples of the (meth) acrylate having an aromatic ring include benzyl acrylate and phenoxy polyethylene glycol acrylate.
Examples of the (meth) acrylic monomer having no hydrogen-bonding functional group in the side chain include, in addition to the above-mentioned compounds: isobornyl (meth) acrylate, cyclohexyl (meth) acrylate; 1, 6-hexanediol dimethacrylate, 1, 9-nonanediol diacrylate, neopentyl glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate; trimethylolpropane triacrylate, pentaerythritol tetramethacrylate, tris (2-acryloyloxyethyl) phosphate, tetramethylolmethane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, and the like. The compounds may be used alone in1 kind or in combination of 2 or more kinds.
By using the above-described preferable compound as the (meth) acrylic monomer, the balance of the properties of the interlayer film such as sound insulation properties is further improved.
From the viewpoint of effectively improving the sound-insulating property, the weight average molecular weight of the (meth) acrylic polymer (1) is preferably 25 ten thousand or more, more preferably 30 ten thousand or more, further preferably 40 ten thousand or more, and particularly preferably 50 ten thousand or more. From the viewpoint of effectively improving the interlayer adhesion, the weight average molecular weight of the (meth) acrylic polymer (1) is preferably 220 ten thousand or less, more preferably 200 ten thousand or less, further preferably 190 ten thousand or less, and particularly preferably 180 ten thousand or less.
The weight average molecular weight means a weight average molecular weight in polystyrene measured by Gel Permeation Chromatography (GPC).
The method for synthesizing the (meth) acrylic polymer (1) by polymerizing the polymerizable composition is not particularly limited. Examples of the synthesis method include solution polymerization, suspension polymerization, and UV polymerization. The method for producing the (meth) acrylic polymer (1) may be a solution polymerization method, a suspension polymerization method, or a UV polymerization method. The method for producing the (meth) acrylic polymer (1) may be a solution polymerization method, may be a method other than the solution polymerization method, and may be a suspension polymerization method or a UV polymerization method.
The method for synthesizing the (meth) acrylic polymer (1) is preferably a solution polymerization method or a UV polymerization method from the viewpoint of improving the transparency of the interlayer film and effectively improving the sound insulation property and the interlayer adhesion in the interlayer film having improved transparency. When the method for synthesizing the (meth) acrylic polymer (1) is a suspension polymerization method, the haze of a laminated glass having an interlayer tends to be increased. When the method for synthesizing the (meth) acrylic polymer (1) is a solution polymerization method or a UV polymerization method, the haze of a laminated glass having an interlayer film is greatly reduced.
However, even if the method for synthesizing the (meth) acrylic polymer (1) is a suspension polymerization method, the haze of the laminated glass having an interlayer film can be reduced by appropriately selecting a surfactant and a dispersant. The dispersant used when the (meth) acrylic polymer (1) is synthesized by a suspension polymerization method is preferably a polymeric dispersant or a reactive surfactant from the viewpoint of adhesiveness. When the dispersant is a polymer dispersant, the dispersant is less likely to migrate to another layer when the interlayer film is laminated, and the interlayer adhesion can be inhibited from being reduced by bleeding of the dispersant to the layer interface or the glass interface. Examples of the polymer dispersant include a block copolymer of ethylene oxide and propylene oxide.
From the viewpoint of effectively improving the sound-insulating property and the interlayer adhesion, the proportion of the structural unit derived from the monomer a in 100 mol% of the total structural units of the (meth) acrylic polymer (1) is preferably 0.1 mol% or more, more preferably 0.2 mol% or more, still more preferably 0.4 mol% or more, and particularly preferably 0.5 mol% or more. From the viewpoint of effectively improving the sound-insulating property and the interlayer adhesion, the proportion of the structural unit derived from the monomer a in 100 mol% of the total structural units of the (meth) acrylic polymer (1) is preferably 50 mol% or less, more preferably 45 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less, and most preferably 30 mol% or less. The (meth) acrylic polymer (1) preferably contains the structural unit derived from the monomer a in this preferred ratio. When the ratio of the structural unit derived from the monomer a is not more than the upper limit, intermolecular hydrogen bonding of the (meth) acrylic polymer derived from the monomer a can be suppressed, and the interlayer adhesion can be suppressed from being weakened.
The (meth) acrylic polymer (1) includes a copolymer of a (meth) acrylic monomer having no hydrogen-bonding functional group in the side chain, a monomer A, and a polymerizable compound (copolymerization component) other than these compounds. The polymerizable composition may contain a (meth) acrylic monomer having no hydrogen-bonding functional group in the side chain and a polymerizable compound other than the monomer a. In the polymerizable composition, the polymerizable compound preferably contains, as a main component, (meth) acrylic monomers having no hydrogen-bonding functional group in the side chain. The proportion of the structural unit (backbone) derived from a (meth) acrylic monomer having no hydrogen-bonding functional group in the side chain is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol% or more, of 100 mol% of the total structural units (backbone) of the (meth) acrylic polymer (1). Examples of polymerizable compounds other than the (meth) acrylic monomer having no hydrogen-bonding functional group in the side chain include vinyl acetate, styrene compounds, and isoprene compounds.
Examples of the polymerizable compound other than the (meth) acrylic monomer having no hydrogen-bonding functional group in the side chain include styrene, vinyl benzoate, and allyl benzoate. By using these polymerizable compounds, when the
Examples of polymerizable compounds other than the (meth) acrylic acid monomer having no hydrogen-bonding functional group in the side chain include polyoxyethylene styrenated propenyl phenyl ether sulfate ammonium, polyoxyethylene nonyl propenyl phenyl ether sulfate ammonium, polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium, polyoxyethylene styrenated propenyl phenyl ether, and polyoxyethylene-1- (allyloxymethyl) alkyl ether. When these polymerizable compounds are used as the reactive surfactant, an intermediate film having high transparency can be obtained even in the case of the suspension polymerization method.
The following methods can be mentioned as a method for analyzing the functional group from the intermediate film. In the case where the intermediate film is a multilayer intermediate film including, for example, the 1 st, 2 nd and 3 rd layers, the 1 st layer is separated from the 2 nd and 3 rd layers from the multilayer intermediate film to obtain the 1 st layer. In the case where the interlayer is a single-layer interlayer provided with only the 1 st layer, the interlayer itself is the 1 st layer. After dissolving the
In the case of a laminated glass, the laminated glass may be cooled by liquid nitrogen or the like, and then the laminated glass member and the interlayer film may be peeled off, and the obtained interlayer film may be used to perform the above analysis.
The content of the vinyl monomer polymer in 100 wt% of the composition of the
When the curable compound for forming the vinyl monomer polymer in the layer containing the vinyl monomer polymer is a photocurable compound having a (meth) acryloyl group, a photocurable apparatus such as an ultraviolet irradiation apparatus is preferably used in order to cure the photocurable compound. Examples of the ultraviolet irradiation device include a box type and a conveyor belt type. Examples of the lamp provided in the ultraviolet irradiation device include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a chemical lamp, a metal halide lamp, an excimer lamp, and a UV-LED. The ultraviolet lamp is preferably a chemical lamp or a UV-LED.
When the photocurable compound is irradiated with ultraviolet light to obtain the vinyl monomer polymer, the amount of ultraviolet light irradiation (cumulative amount of irradiation) is preferably 500mJ or more, more preferably 1000mJ or more, even more preferably 1500mJ or more, and particularly preferably 2000mJ or more. The ultraviolet irradiation amount (cumulative irradiation amount) is preferably 20000mJ or less, more preferably 10000mJ or less, and further preferably 8000mJ or less. When the ultraviolet irradiation amount (cumulative irradiation amount) is not less than the lower limit, the amount of unreacted monomers can be reduced. When the ultraviolet irradiation amount (cumulative irradiation amount) is not more than the upper limit, the storage stability of the resin is improved. The irradiation intensity of the ultraviolet irradiation is 0.1mW or more, preferably 0.5mW or more, more preferably 1mW or more, and further preferably 2mW or more.
The 1 st layer may contain a thermoplastic resin other than the vinyl monomer polymer (1). The 1 st layer may contain a polyvinyl acetal resin (hereinafter, sometimes referred to as polyvinyl acetal resin (1)).
When the 1 st layer contains the vinyl monomer polymer (1) and the polyvinyl acetal resin (1), the following preferable content is preferably satisfied. The content of the vinyl monomer polymer (1) is preferably 1% by weight or more, more preferably 10% by weight or more, further preferably 20% by weight or more, and particularly preferably 50% by weight or more, based on 100% by weight of the total of the vinyl monomer polymer (1) and the polyvinyl acetal resin (1). The content of the vinyl monomer polymer (1) is preferably 99% by weight or less, more preferably 90% by weight or less, and still more preferably 80% by weight or less, based on 100% by weight of the total of the vinyl monomer polymer (1) and the polyvinyl acetal resin (1). When the content is not more than the upper limit, the interlayer adhesion is further improved. When the content is not less than the lower limit, the sound insulation of the laminated glass is further improved.
The 2 nd layer preferably contains a thermoplastic resin (hereinafter, may be referred to as thermoplastic resin (2)). In the 2 nd layer, the thermoplastic resin (2) preferably contains a polyvinyl acetal resin (hereinafter, may be referred to as a polyvinyl acetal resin (2)). The 3 rd layer preferably contains a thermoplastic resin (hereinafter, sometimes referred to as thermoplastic resin (3)). In the
The thermoplastic resin is a resin that softens and exhibits plasticity when heated and solidifies when cooled to room temperature. The thermoplastic elastomer is a resin that softens and develops plasticity when heated and solidifies and develops rubber elasticity when cooled to room temperature (25 ℃).
Examples of the thermoplastic resin include: polyvinyl acetal resins, polyester resins, aliphatic polyolefins, polystyrenes, ethylene-vinyl acetate copolymer resins, ethylene-acrylic acid copolymer resins, polyurethane resins, ionomer resins, polyvinyl alcohol resins, polyvinyl acetate resins, and the like. Thermoplastic resins other than these may also be used.
The thermoplastic resin mentioned above can be a thermoplastic elastomer by adjusting the molecular structure, polymerization degree, and the like of the resin.
The polyvinyl acetal resin is preferably an acetal compound of polyvinyl alcohol. The polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate. The saponification degree of the polyvinyl alcohol is usually 70 to 99.9 mol%.
The polyvinyl alcohol (PVA) has an average polymerization degree of preferably 200 or more, more preferably 500 or more, further preferably 1500 or more, further preferably 1600 or more, particularly preferably 2600 or more, most preferably 2700 or more, preferably 5000 or less, more preferably 4000 or less, further preferably 3500 or less. When the average polymerization degree is not less than the lower limit, the penetration resistance and bending rigidity of the laminated glass are further improved. When the average polymerization degree is not more than the upper limit, the intermediate film can be easily formed.
The average polymerization degree of the polyvinyl alcohol is determined by a method based on JIS K6726 "polyvinyl alcohol test method".
The carbon number of the acetal group in the polyvinyl acetal resin is preferably 2 to 10, more preferably 2 to 5, and further preferably 2, 3, or 4. In addition, the number of carbon atoms of the acetal group in the polyvinyl acetal resin is preferably 2 or 4, and in this case, the production of the polyvinyl acetal resin is relatively efficient.
As the aldehyde, an aldehyde having 1 to 10 carbon atoms is generally preferably used. Examples of the aldehyde having 1 to 10 carbon atoms include: formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexanal, n-octylaldehyde, n-nonanal, n-decanal, p-isopropylbenzaldehyde, benzaldehyde and the like. Acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexanal, or n-valeraldehyde is preferred. Acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, or n-valeraldehyde is more preferred, and acetaldehyde, n-butyraldehyde, or n-valeraldehyde is further preferred. The aldehydes may be used alone in1 kind or in combination of 2 or more kinds.
The respective content ratios of the hydroxyl groups in the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) are preferably 25 mol% or more, preferably 38 mol% or less, more preferably 35 mol% or less, further preferably 32 mol% or less, particularly preferably 30 mol% or less, and most preferably 27.5 mol% or less. When the content of the hydroxyl group is not less than the lower limit, the adhesive strength of the interlayer film is further improved. When the content of the hydroxyl group is not more than the upper limit, the flexibility of the interlayer film is improved, and the interlayer film can be easily handled. When the content of the hydroxyl group is not more than the upper limit, the rigidity is effectively improved.
The content of hydroxyl groups in the polyvinyl acetal resin is a value represented by a percentage of a molar fraction obtained by dividing the amount of ethylene groups to which hydroxyl groups are bonded by the total amount of ethylene groups in the main chain. The amount of the above-mentioned ethylene group to which a hydroxyl group is bonded can be measured, for example, by "polyvinyl butyral test method" in accordance with JIS K6728.
The degree of acetylation of each of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 0.01 mol% or more, more preferably 0.5 mol% or more, preferably 10 mol% or less, and more preferably 2 mol% or less. When the acetylation degree is not less than the lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is improved. When the acetylation degree is not more than the upper limit, the moisture resistance of the interlayer film and the laminated glass is improved.
The acetylation degree is a value represented by a percentage of a molar fraction obtained by dividing the amount of ethylene groups to which acetyl groups are bonded by the total amount of ethylene groups in the main chain. The amount of the ethylene group to which the acetyl group is bonded can be measured, for example, in accordance with JIS K6728 "test method for polyvinyl butyral".
The acetalization degree (butyralization degree in the case of a polyvinyl butyral resin) of each of the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 55 mol% or more, more preferably 67 mol% or more, preferably 75 mol% or less, and more preferably 71 mol% or less. When the acetalization degree is not less than the lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is improved. When the acetalization degree is not more than the upper limit, the reaction time required for producing the polyvinyl acetal resin becomes short.
The acetalization degree is obtained as follows. First, a value obtained by subtracting the amount of the hydroxyl group-bonded ethylene group and the acetyl group-bonded ethylene group from the total ethylene group amount of the main chain was obtained. The molar fraction was determined by dividing the obtained value by the total ethylene amount of the main chain. The value of the mole fraction expressed as a percentage is the acetalization degree.
The content of the hydroxyl group (amount of hydroxyl group), the acetalization degree (butyralization degree) and the acetylation degree are preferably calculated from the results obtained by measurement in accordance with JIS K6728 "test method for polyvinyl butyral". However, measurements based on ASTM D1396-92 can also be used. When the polyvinyl acetal resin is a polyvinyl butyral resin, the content of the hydroxyl groups (amount of hydroxyl groups), the acetalization degree (butyralization degree) and the acetylation degree can be calculated from the results obtained by the measurement according to JIS K6728 "polyvinyl butyral test method".
(plasticizer)
The intermediate film preferably comprises a plasticizer. The layer 1 (including the single-layer interlayer) preferably contains a plasticizer (hereinafter, referred to as plasticizer (1)) in some cases. The 2 nd layer preferably contains a plasticizer (hereinafter, may be referred to as plasticizer (2)). The 3 rd layer preferably contains a plasticizer (hereinafter, referred to as plasticizer (3)) in some cases. By using a plasticizer or by using a polyvinyl acetal resin and a plasticizer in combination, the penetration resistance is further improved, and the adhesion of a layer containing a polyvinyl acetal resin and a plasticizer to a laminated glass member or another layer is appropriately improved. The plasticizer is not particularly limited. The plasticizer (1), the plasticizer (2) and the plasticizer (3) may be the same or different. The plasticizer (1), the plasticizer (2) and the plasticizer (3) may be used alone or in combination of 1 or more.
Examples of the plasticizer include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and organic phosphoric acid plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers. The plasticizer is preferably an organic ester plasticizer. The plasticizer is preferably a liquid plasticizer.
Examples of the monobasic organic acid ester include glycol esters obtained by the reaction of a glycol and a monobasic organic acid. Examples of the diol include triethylene glycol, tetraethylene glycol, and tripropylene glycol. Examples of the monobasic organic acid include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, n-nonanoic acid, decanoic acid, and the like.
The polybasic organic acid ester includes ester compounds of a polybasic organic acid and an alcohol having a linear or branched structure having 4 to 8 carbon atoms. Examples of the polyvalent organic acid include adipic acid, sebacic acid, azelaic acid and the like.
Examples of the organic ester plasticizer include: triethylene glycol di-2-ethylpropionate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-caprylate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol oxalate, ethylene glycol di-2-ethylbutyrate, 1, 3-propanediol di-2-ethylbutyrate, 1, 4-butanediol di-2-ethylbutyrate, diethylene glycol di-2-ethylhexanoate, dipropylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylvalerate, tetraethylene glycol di-2-ethylbutyrate, and mixtures thereof, Diethylene glycol dicaprylate, dibutyl maleate, bis (2-butoxyethyl) adipate, dibutyl adipate, diisobutyl adipate, 2-butoxyethoxyethyl adipate, glycol benzoate, 1, 3-butanediol adipate polyester, dihexyl adipate, dioctyl adipate, hexylcyclohexyl adipate, a mixture of heptyl and nonyl adipates, diisononyl adipate, diisodecyl adipate, heptylnonyl adipate, tributyl citrate, tributyl acetylcitrate, diethyl carbonate, dibutyl sebacate, oil-modified sebacic acid, and a mixture of phosphate esters and adipate. Organic ester plasticizers other than these may also be used. Adipates other than those mentioned above may also be used.
Examples of the organic phosphoric acid plasticizer include tributoxyethyl phosphate, isodecylphenyl phosphate, tricresyl phosphate, triisopropyl phosphate, and the like.
The plasticizer may be a diester plasticizer represented by the following formula (1).
[ chemical formula 1]
In the formula (1), R1 and R2 respectively represent an organic group having 2-10 carbon atoms, R3 represents an ethylene group, an isopropylene group or an n-propylene group, and p represents an integer of 3-10. R1 and R2 in the formula (1) are respectively preferably organic groups with 5-10 carbon atoms, and more preferably organic groups with 6-10 carbon atoms.
In the case where the
In the
When the (meth) acrylic polymer (1) is contained in the 1 st layer, the plasticizer in the 1 st layer preferably contains an organic ester plasticizer.
In the 1 st layer, the content of the plasticizer (1) with respect to 100 parts by weight of the (meth) acrylic polymer (1) is defined as content (1 b). The content (1b) is preferably 15 parts by weight or more, more preferably 20 parts by weight or more, preferably 60 parts by weight or less, more preferably 55 parts by weight or less, and further preferably 50 parts by weight or less. When the content (1b) is not less than the lower limit, the flexibility of the interlayer film is improved, and the interlayer film can be easily handled. When the content (1b) is not more than the upper limit, the penetration resistance of the laminated glass is further improved.
When the 1 st layer contains the polyvinyl acetal resin (1), the content of the plasticizer (1) to 100 parts by weight of the total of the vinyl monomer polymer (1) and the polyvinyl acetal resin (1) is defined as content (1A). The content (1A) is preferably 50 parts by weight or more, more preferably 55 parts by weight or more, further preferably 60 parts by weight or more, preferably 100 parts by weight or less, more preferably 90 parts by weight or less, further preferably 85 parts by weight or less, and particularly preferably 80 parts by weight or less. When the content (1A) is not less than the lower limit, the flexibility of the interlayer film is improved, and the interlayer film can be easily handled. When the content (1A) is not more than the upper limit, the penetration resistance of the laminated glass is further improved.
In the 2 nd layer, the content of the plasticizer (2) is defined as content (2) with respect to 100 parts by weight of the thermoplastic resin (2) (in the case where the thermoplastic resin (2) is a polyvinyl acetal resin (2), 100 parts by weight of the polyvinyl acetal resin (2)). In the 3 rd layer, the content of the plasticizer (3) is defined as content (3) with respect to 100 parts by weight of the thermoplastic resin (3) (in the case where the thermoplastic resin (3) is a polyvinyl acetal resin (3), 100 parts by weight of the polyvinyl acetal resin (3)). The content (2) and the content (3) are each preferably 5 parts by weight or more, more preferably 10 parts by weight or more, further preferably 15 parts by weight or more, further preferably 20 parts by weight or more, particularly preferably 24 parts by weight or more, and most preferably 25 parts by weight or more. The content (2) and the content (3) are each preferably 50 parts by weight or less, more preferably 45 parts by weight or less, still more preferably 40 parts by weight or less, particularly preferably 37 parts by weight or less, and most preferably 35 parts by weight or less. When the content (2) and the content (3) are not less than the lower limit, the flexibility of the interlayer film is improved, and the interlayer film can be easily handled. When the content (2) and the content (3) are not more than the upper limit, the penetration resistance of the laminated glass is further improved.
In the 1 st layer, the content of the plasticizer (1) to 100 parts by weight of the vinyl monomer polymer (1) is defined as content (1). From the viewpoint of effectively improving the sound-insulating property of the laminated glass, the content (1) is preferably higher than the content (2), and the content (1) is preferably higher than the content (3).
From the viewpoint of further improving the sound-insulating property of the laminated glass, the absolute value of the difference between the content (2) and the content (1) and the absolute value of the difference between the content (3) and the content (1) are each preferably 5 parts by weight or more, more preferably 10 parts by weight or more, still more preferably 15 parts by weight or more, and still more preferably 20 parts by weight or more. The absolute value of the difference between the content (2) and the content (1) and the absolute value of the difference between the content (3) and the content (1) are each preferably 80 parts by weight or less, more preferably 75 parts by weight or less, and still more preferably 70 parts by weight or less.
(Heat insulating Material)
The intermediate film may contain a heat insulating substance. The 1 st layer may contain a thermally insulating substance. The 2 nd layer may contain a heat insulating substance. The 3 rd layer may contain a heat insulating substance. The heat insulating material may be used alone in1 kind or in combination of 2 or more kinds.
The heat insulating substance may include at least 1 component X of phthalocyanine compounds, naphthalocyanine compounds, and anthracyanine compounds, or heat insulating particles. In this case, the heat insulating substance may contain both the component X and the heat insulating particles.
The intermediate film may contain at least 1 component X of a phthalocyanine compound, a naphthalocyanine compound, and an anthracyanine compound. The 1 st layer may contain the component X. The 2 nd layer may contain the component X. The 3 rd layer may contain the component X. The component X is a heat-insulating substance. The component X may be used alone in1 kind or in combination of 2 or more kinds.
The component X is not particularly limited. As the component X, conventionally known phthalocyanine compounds, naphthalocyanine compounds and anthracene phthalocyanine compounds can be used.
Examples of the component X include phthalocyanine, phthalocyanine derivatives, naphthalocyanine derivatives, anthracyanine and anthracyanine derivatives. The phthalocyanine compound and the derivative of phthalocyanine each preferably have a phthalocyanine skeleton. The naphthalocyanine compound and the derivative of naphthalocyanine each preferably have a naphthalocyanine skeleton. The anthracene phthalocyanine compound and the derivative of anthracene phthalocyanine each preferably have an anthracene phthalocyanine skeleton.
The component X may contain a vanadium atom or a copper atom. The component X may contain a vanadium atom and may contain a copper atom. The component X may be at least 1 of phthalocyanine containing a vanadium atom or a copper atom and a derivative of phthalocyanine containing a vanadium atom or a copper atom.
The intermediate film may include thermal insulating particles. The
As the heat insulating particles, metal oxide particles may be used. As the heat insulating particles, particles formed of an oxide of a metal (metal oxide particles) can be used.
Infrared rays having a wavelength longer than that of visible light, i.e., 780nm or more, have smaller energy than ultraviolet rays. However, infrared rays have a large thermal action, and are emitted as heat when absorbed by a substance. Therefore, the infrared ray is generally called a hot ray. By using the heat insulating particles, infrared rays (heat rays) can be effectively blocked. The heat insulating particles are particles that absorb infrared rays.
Specific examples of the heat-insulating particles include: aluminum-doped tin oxide particles, indium-doped tin oxide particles, antimony-doped tin oxide particles (ATO particles), gallium-doped zinc oxide particles (GZO particles), indium-doped zinc oxide particles (IZO particles), aluminum-doped zinc oxide particles (AZO particles), niobiumMetal oxide particles such as doped titanium oxide particles, sodium-doped tungsten oxide particles, cesium-doped tungsten oxide particles, thallium-doped tungsten oxide particles, rubidium-doped tungsten oxide particles, tin-doped indium oxide particles (ITO particles), tin-doped zinc oxide particles, and silicon-doped zinc oxide particles, and lanthanum hexaboride (LaB)6) Particles, and the like. Insulating particles other than these may be used.
(Metal salt)
The intermediate film may contain at least 1 metal salt (hereinafter, sometimes referred to as metal salt M) of an alkali metal salt, an alkaline earth metal salt, and a magnesium salt. The 1 st layer may include the metal salt M. The 2 nd layer may include the metal salt M. The 3 rd layer may include the metal salt M. The use of the metal salt M facilitates control of the adhesiveness between the interlayer and a laminated glass member such as a glass plate or the adhesiveness between the interlayer and each other. The metal salt M may be used alone in1 kind or in combination of 2 or more kinds.
The metal salt M may contain at least 1 metal selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba.
The metal salt M may be an alkali metal salt of an organic acid having 2 to 16 carbon atoms, an alkaline earth metal salt of an organic acid having 2 to 16 carbon atoms, or a magnesium salt of an organic acid having 2 to 16 carbon atoms.
Examples of the magnesium carboxylate having 2 to 16 carbon atoms and the potassium carboxylate having 2 to 16 carbon atoms include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutyrate, potassium 2-ethylbutyrate, magnesium 2-ethylhexanoate, and potassium 2-ethylhexanoate.
(ultraviolet screening agent)
The intermediate film may include an ultraviolet shielding agent. The 1 st layer may contain an ultraviolet shielding agent. The 2 nd layer may contain an ultraviolet shielding agent. The 3 rd layer may contain a uv-screening agent. By using the ultraviolet shielding agent, the visible light transmittance is further reduced less even if the interlayer film and the laminated glass are used for a long period of time. The ultraviolet screening agent may be used alone in1 kind or in combination of 2 or more kinds.
The ultraviolet screening agent contains an ultraviolet absorber. The ultraviolet screening agent is preferably an ultraviolet absorber.
Examples of the ultraviolet shielding agent include an ultraviolet shielding agent containing a metal atom, an ultraviolet shielding agent containing a metal oxide, an ultraviolet shielding agent having a benzotriazole structure (benzotriazole compound), an ultraviolet shielding agent having a benzophenone structure (benzophenone compound), an ultraviolet shielding agent having a triazine structure (triazine compound), an ultraviolet shielding agent having a malonate structure (malonate compound), an ultraviolet shielding agent having an oxalic anilide structure (oxalic anilide compound), and an ultraviolet shielding agent having a benzoate structure (benzoate compound).
Examples of the ultraviolet shielding agent containing a metal atom include platinum particles, particles in which the surface of platinum particles is coated with silica, palladium particles, and particles in which the surface of palladium particles is coated with silica. The ultraviolet shielding agent is preferably not a heat insulating particle.
Examples of the ultraviolet shielding agent containing a metal oxide include zinc oxide, titanium oxide, and cerium oxide. Further, in the case of the ultraviolet shielding agent containing a metal oxide, the surface may be coated. Examples of the coating material for the surface of the ultraviolet shielding agent containing a metal oxide include an insulating metal oxide, a hydrolyzable organosilicon compound, and a polysiloxane compound.
Examples of the insulating metal oxide include silica, alumina, zirconia, and the like. The insulating metal oxide has a band gap energy of, for example, 5.0eV or more.
Examples of the ultraviolet-screening agent having a benzotriazole structure include: 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole ("Tinuvin P" manufactured by BASF corporation), 2- (2 '-hydroxy-3', 5 '-di-tert-butylphenyl) benzotriazole ("Tinuvin 320" manufactured by BASF corporation), 2- (2' -hydroxy-3 '-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole ("Tinuvin 326" manufactured by BASF corporation), and 2- (2' -hydroxy-3 ', 5' -dipentylphenyl) benzotriazole ("Tinuvin 328" manufactured by BASF corporation).
Examples of the ultraviolet shielding agent having a benzophenone structure include OCTABENZONE ("Chimassorb 81" manufactured by BASF corporation).
Examples of the ultraviolet-screening agent having a triazine structure include "LA-F70" manufactured by ADEKA, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [ (hexyl) oxy ] -phenol ("Tinuvin 1577 FF" manufactured by BASF), and the like.
Examples of the ultraviolet-screening agent having a malonate structure include dimethyl 2- (p-methoxybenzylidene) malonate,
Examples of commercially available products of the above-mentioned ultraviolet screening agents having a malonate structure include Hostavin B-CAP, Hostavin PR-25 and Hostavin PR-31 (both manufactured by CLARIANT Co., Ltd.).
Examples of the ultraviolet-screening agent having an oxalic acid aniline structure include: oxalic acid diamides having an aryl group substituted on a nitrogen atom, such as N- (2-ethylphenyl) -N ' - (2-ethoxy-5-tert-butylphenyl) oxalic acid diamide, N- (2-ethylphenyl) -N ' - (2-ethoxy-phenyl) oxalic acid diamide, and 2-ethyl-2 ' -ethoxy-oxyaniline ("Sanduvor VSU" manufactured by CLARIANT).
Examples of the ultraviolet-screening agent having a benzoate structure include 2, 4-di-tert-butylphenyl-3, 5-di-tert-butyl-4-hydroxybenzoate ("Tinuvin 120" manufactured by BASF corporation) and the like.
(antioxidant)
The intermediate film may comprise an antioxidant. The
Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. The phenolic antioxidant is an antioxidant with a phenolic skeleton. The sulfur antioxidant is an antioxidant containing a sulfur atom. The phosphorus antioxidant is an antioxidant containing a phosphorus atom.
Examples of the phenolic antioxidant include: 2, 6-di-t-butyl-p-cresol (BHT), Butylhydroxyanisole (BHA), 2, 6-di-t-butyl-4-ethylphenol, stearyl- β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, 2 ' -methylenebis- (4-methyl-6-butylphenol), 2 ' -methylenebis- (4-ethyl-6-t-butylphenol), 4 ' -butylidene-bis- (3-methyl-6-t-butylphenol), 1, 3-tris- (2-methyl-hydroxy-5-t-butylphenyl) butane, tetrakis [ methylene-3- (3 ', 5 ' -butyl-4-hydroxyphenyl) propionate ] methane, tetrahydroxytoluene (BHA), Butylhydroxyanisole (BHA), 2, 6-di-t-butyl-4-ethylphenol, stearyl- β - (3, 5-di, 1,3, 3-tris- (2-methyl-4-hydroxy-5-tert-butylphenol) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, ethylene glycol bis (3, 3' -tert-butylphenol) butyrate, and ethylene bis (oxyethylene) bis (3-tert-butyl-4-hydroxy-5-methylpropanoic acid), and the like. It is preferable to use 1 or 2 or more of these antioxidants.
Examples of the phosphorus-based antioxidant include: tridecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, bis (tridecyl) pentaerythritol diphosphite, bis (decyl) pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butyl-6-methylphenyl) ethyl phosphite, and 2, 2' -methylenebis (4, 6-di-tert-butyl-1-phenoxy) (2-ethylhexyloxy) phosphorus. It is preferable to use 1 or 2 or more of these antioxidants.
Examples of commercially available products of the antioxidant include: "IRGANOX 245" manufactured by BASF, "IRGAFOS 168" manufactured by BASF, "IRGAFOS 38" manufactured by BASF, "SUMILIZERBHT" manufactured by Sumitomo chemical industry, "H-BHT" manufactured by Sakai chemical industry, and "IRGANOX 1010" manufactured by BASF.
(other Components)
The intermediate film, the 1 st layer, the 2 nd layer, and the 3 rd layer may contain additives such as a coupling agent, a dispersant, a surfactant, a flame retardant, an antistatic agent, a pigment, a dye, an adhesion adjuster other than a metal salt, a moisture resistant agent, a fluorescent whitening agent, and an infrared absorber, as required. These additives may be used alone in1 kind or in combination of 2 or more kinds.
(other details of the intermediate film)
The thickness of the intermediate film is not particularly limited. From the viewpoint of practical use and from the viewpoint of sufficiently improving penetration resistance and bending rigidity of the laminated glass, the thickness of the interlayer film is preferably 0.1mm or more, more preferably 0.25mm or more, preferably 3mm or less, and more preferably 1.5mm or less. When the thickness of the interlayer film is not less than the lower limit, penetration resistance and bending rigidity of the laminated glass are further improved. When the thickness of the interlayer film is not more than the upper limit, the transparency of the interlayer film becomes further excellent.
The thickness of the interlayer film was T. The thickness of the 1 st layer is preferably 0.035T or more, more preferably 0.0625T or more, further preferably 0.1T or more, preferably 0.4T or less, more preferably 0.375T or less, further preferably 0.25T or less, and particularly preferably 0.15T or less. When the thickness of the 1 st layer is 0.4T or less, the bending rigidity is further improved.
The thickness of each of the 2 nd layer and the 3 rd layer is preferably 0.3T or more, more preferably 0.3125T or more, further preferably 0.375T or more, preferably 0.97T or less, more preferably 0.9375T or less, and further preferably 0.9T or less. The thicknesses of the 2 nd layer and the 3 rd layer may be 0.46875T or less, or 0.45T or less. When the thicknesses of the 2 nd layer and the 3 rd layer are not less than the lower limit and not more than the upper limit, the rigidity of the laminated glass is further improved.
The total thickness of the 2 nd layer and the 3 rd layer is preferably 0.625T or more, more preferably 0.75T or more, further preferably 0.85T or more, preferably 0.97T or less, more preferably 0.9375T or less, further preferably 0.9T or less. When the total thickness of the 2 nd layer and the 3 rd layer is not less than the lower limit and not more than the upper limit, the rigidity of the laminated glass is further improved.
The intermediate film may be a uniform thickness intermediate film or a variable thickness intermediate film. The cross-sectional shape of the intermediate film may be rectangular or wedge-shaped.
The method for producing the intermediate film of the present invention is not particularly limited. Examples of the method for producing an interlayer film of the present invention include: a method of forming each layer using each resin composition for forming each layer, and then laminating the obtained layers; and a method of laminating the respective layers by co-extruding the respective resin compositions for forming the respective layers using an extruder. Since the method is suitable for continuous production, a production method by extrusion molding is preferable.
From the viewpoint of excellent production efficiency of the intermediate film, it is preferable that the 2 nd layer and the 3 rd layer contain the same polyvinyl acetal resin. From the viewpoint of excellent production efficiency of the intermediate film, it is more preferable that the 2 nd layer and the 3 rd layer contain the same polyvinyl acetal resin and the same plasticizer. From the viewpoint of excellent production efficiency of the intermediate film, it is more preferable that the 2 nd layer and the 3 rd layer are formed of the same resin composition.
The intermediate film preferably has a concavo-convex shape on at least one of both surfaces. The intermediate film more preferably has a concavo-convex shape on both surfaces. The method for forming the above-described uneven shape is not particularly limited, and examples thereof include lip embossing, embossing roll method, calender roll method, profile extrusion method, and the like. The embossing roll method is preferable because a plurality of concave and convex shapes can be quantitatively formed as a certain concave and convex pattern.
(laminated glass)
The laminated glass of the present invention comprises a1 st laminated glass member, a2 nd laminated glass member, and the interlayer film for laminated glass. In the laminated glass of the present invention, the interlayer film for laminated glass is disposed between the 1 st laminated glass member and the 2 nd laminated glass member.
The laminated glass of the present invention comprises a1 st laminated glass member, a2 nd laminated glass member, and an interlayer film for laminated glass disposed between the 1 st laminated glass member and the 2 nd laminated glass member. In the laminated glass of the present invention, the interlayer film includes the
Fig. 3 is a cross-sectional view schematically showing an example of a laminated glass using the interlayer film for laminated glass shown in fig. 1.
The
The 1 st
Fig. 4 is a cross-sectional view schematically showing an example of a laminated glass using the interlayer film for a laminated glass shown in fig. 2.
The laminated glass 31A shown in fig. 4 includes the 1 st
The 1 st
As described above, the laminated glass of the present invention includes the 1 st laminated glass member, the 2 nd laminated glass member, and the interlayer film, which is the interlayer film for laminated glass of the present invention. In the laminated glass of the present invention, the interlayer film is disposed between the 1 st laminated glass member and the 2 nd laminated glass member.
The 1 st laminated glass member is preferably a1 st glass plate. The 2 nd laminated glass member is preferably a2 nd glass plate.
Examples of the 1 st and 2 nd laminated glass members include a glass plate and a PET (polyethylene terephthalate) film. The laminated glass includes not only a laminated glass in which an interlayer film is interposed between 2 glass plates but also a laminated glass in which an interlayer film is interposed between a glass plate and a PET film or the like. The laminated glass is a laminate comprising glass plates, and preferably at least 1 glass plate is used. The 1 st laminated glass member and the 2 nd laminated glass member are each a glass plate or a PET film, and the laminated glass preferably includes a glass plate as at least one of the 1 st laminated glass member and the 2 nd laminated glass member. In particular, both of the 1 st and 2 nd laminated glass members are preferably glass plates.
Examples of the glass plate include inorganic glass and organic glass. Examples of the inorganic glass include a float glass plate, a heat ray absorbing glass plate, a heat ray reflecting glass plate, a polished glass plate, a mother glass, and a wired glass. The organic glass is synthetic resin glass which replaces inorganic glass. Examples of the organic glass include a polycarbonate plate and a poly (meth) acrylic resin plate. Examples of the poly (meth) acrylic resin plate include a poly (methyl (meth) acrylate plate and the like.
The thickness of each of the 1 st laminated glass member and the 2 nd laminated glass member is preferably 1mm or more, preferably 5mm or less, and more preferably 3mm or less. When the laminated glass member is a glass plate, the thickness of the glass plate is preferably 0.5mm or more, more preferably 0.7mm or more, preferably 5mm or less, and more preferably 3mm or less. When the laminated glass member is a PET film, the thickness of the PET film is preferably 0.03mm or more, and preferably 0.5mm or less.
The glass plate may have a thickness of 2mm or less. The thickness of the glass plate may be 1.8mm or less, 1.6mm or less, and 1.0mm or less. When the thickness of the glass sheet is not more than the upper limit, the laminated glass can be reduced in weight, the material of the laminated glass can be reduced to reduce the environmental load, or the fuel efficiency of the vehicle can be improved by reducing the weight of the laminated glass to reduce the environmental load. The sum of the thickness of the 1 st glass plate and the thickness of the 2 nd glass plate may be 3.5mm or less, and may be 2.8mm or less. When the sum of the thickness of the 1 st glass plate and the thickness of the 2 nd glass plate is equal to or less than the upper limit, the laminated glass can be reduced in weight, the environmental load can be reduced by reducing the material of the laminated glass, or the fuel efficiency of the vehicle can be improved and the environmental load can be reduced by reducing the weight of the laminated glass.
The method for producing the laminated glass is not particularly limited. First, an interlayer film is interposed between the 1 st laminated glass member and the 2 nd laminated glass member. Next, air remaining between the 1 st laminated glass member, the 2 nd laminated glass member, and the interlayer film is degassed by, for example, pressing a roller or putting into a rubber bag and performing suction under reduced pressure. Then, pre-pressing at about 70 to 110 ℃ to obtain a laminate. Next, the laminate is placed in an autoclave or pressed, and press-bonded at about 120 to 150 ℃ and a pressure of 1 to 1.5 MPa. Thereby, a laminated glass can be obtained. In the production of the laminated glass, the 1 st, 2 nd and 3 rd layers may be laminated.
The interlayer film and the laminated glass can be used for vehicles, railway vehicles, spacecrafts, ships, buildings and the like. The interlayer film and the laminated glass can be used for other applications. The interlayer film and the laminated glass are preferably an interlayer film and a laminated glass for a vehicle or for a building, and more preferably an interlayer film and a laminated glass for a vehicle. The interlayer film and the laminated glass can be used for windshields, side glass, rear glass, roof glass and the like of vehicles. The interlayer film and the laminated glass are preferably used for vehicles. The intermediate film is used for obtaining laminated glass of a vehicle.
The present invention will be described in more detail below with reference to examples and comparative examples. The present invention is not limited to these examples.
The following materials were prepared.
In addition, the acetalization degree (butyralization degree), acetylation degree and hydroxyl group content of the polyvinyl acetal resin were measured by methods based on JIS K6728 "polyvinyl butyral test method". When measured by ASTM D1396-92, the same numerical values as those obtained by the method in accordance with JIS K6728 "polyvinyl butyral test method" are shown. In the case where the type of acetal is acetal or the like, the acetalization degree is calculated by measuring the acetylation degree and the content of hydroxyl groups, calculating the molar fraction from the obtained measurement results, and subtracting the acetylation degree and the content of hydroxyl groups from 100 mol%.
(resin)
Polyvinyl acetate and (meth) acrylic polymers represented by:
polyvinyl acetate (1): synthesis example 1
(Synthesis example 1)
A polymerization vessel made of glass and provided with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet was prepared. Into the polymerization vessel were charged 100 parts by weight of a vinyl acetate monomer, 1.0 part by weight of 3-methyl-3-buten-1-ol (MB) and 3.8 parts by weight of methanol, and the inside of the polymerization vessel was purged with nitrogen while heating and stirring. Then, 0.02 part by weight of t-butyl peroxyneodecanoate, 150 parts by weight of a vinyl acetate monomer and 1.5 parts by weight of 3-methyl-3-buten-1-ol (MB) as a polymerization initiator were added dropwise over 4 hours while setting the temperature in the polymerization vessel to 60 ℃, and after the dropwise addition was completed, the mixture was polymerized for 1 hour to obtain a solution containing polyvinyl acetate (1). The solution was dried in an oven at 110 ℃ for 3 hours to obtain polyvinyl acetate (1). In the polyvinyl acetate (1), the proportion of the structural units derived from MB was 0.4 mol%.
Polyvinyl acetate (2): synthesis example 2
(Synthesis example 2)
Polyvinyl acetate (2) was obtained in the same manner as in synthesis example 1, except that 3-methyl-3-buten-1-ol (MB) was changed to ethylene glycol monovinyl ether (HEVE), and the proportion of the structural unit derived from HEVE was changed to 0.4 mol%.
Polyvinyl acetate (3): synthesis example 3
(Synthesis example 3)
Polyvinyl acetate (3) was obtained in the same manner as in synthesis example 1, except that 3-methyl-3-buten-1-ol (MB) was changed to ethylene glycol monovinyl ether (HEVE) and the proportion of the structural unit derived from HEVE was changed to 0.2 mol%.
Polyvinyl acetate (4): synthesis example 4
(Synthesis example 4)
Polyvinyl acetate (4) was obtained in the same manner as in synthesis example 1, except that 3-methyl-3-buten-1-ol (MB) was changed to ethylene glycol monovinyl ether (HEVE) and the proportion of the structural unit derived from HEVE was changed to 10 mol%.
Polyvinyl acetate (5): synthesis example 5
(Synthesis example 5)
Polyvinyl acetate (5) was obtained in the same manner as in synthesis example 1, except that 3-methyl-3-buten-1-ol (MB) was changed to ethylene glycol monovinyl ether (HEVE) and the proportion of the structural unit derived from HEVE was changed to 30 mol%.
Polyvinyl acetate (6): synthesis example 6
(Synthesis example 6)
Polyvinyl acetate (6) was obtained in the same manner as in synthesis example 1, except that 3-methyl-3-buten-1-ol (MB) was changed to Isopropylacrylamide (IPA) and the proportion of the structural unit derived from IPA was changed to 1 mol%.
Polyvinyl acetate (7): synthesis example 7
(Synthesis example 7)
A polymerization vessel made of glass and provided with a reflux condenser, a thermometer and a nitrogen inlet was prepared. The following components were charged into the polymerization vessel, and the inside of the polymerization vessel was replaced with nitrogen while heating and stirring.
230 parts by weight of ion-exchanged water
0.1 part by weight of polyoxyethylene styrenated propenyl phenyl ether sulfate ammonium salt ("AR-30" manufactured by first Industrial pharmaceutical Co., Ltd.)
Vinyl acetate monomer 50 parts by weight
Ethylene glycol monovinyl ether (HEVE)0.5 part by weight
0.08 parts by weight of t-butyl peroxyneodecanoate as a polymerization initiator
Then, the inside of the polymerization vessel was set at 60 ℃ and polymerized for 3 hours to obtain particulate polyvinyl acetate (7).
Polyvinyl acetate (8): synthesis example 8
(Synthesis example 8)
A polymerization vessel made of glass and provided with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet was prepared. The following components were charged into the polymerization vessel, and the inside of the polymerization vessel was replaced with nitrogen while heating and stirring.
230 parts by weight of ion-exchanged water
0.5 part by weight of polyoxyethylene styrenated propenyl phenyl ether sulfate ammonium salt ("AR-30" manufactured by first Industrial pharmaceutical Co., Ltd.)
0.005 part by weight of an ethylene oxide/propylene oxide copolymer ("EP-10" manufactured by Ming Dynasty chemical industries Co., Ltd.)
Next, 0.08 parts by weight of t-butyl peroxyneodecanoate, 47.5 parts by weight of a vinyl acetate monomer, 0.5 parts by weight of ethylene glycol monovinyl ether (HEVE), and 2.5 parts by weight of benzyl acrylate were added as a polymerization initiator to the polymerization vessel at 60 ℃, and polymerized for 6 hours to obtain particulate polyvinyl acetate (8).
(meth) acrylic polymer (9): synthesis example 9
(Synthesis example 9)
A polymerization vessel made of glass and provided with a reflux condenser, a thermometer and a nitrogen inlet was prepared. The following components were charged into the polymerization vessel, and the inside of the polymerization vessel was replaced with nitrogen while heating and stirring.
230 parts by weight of ion-exchanged water
Polyoxyethylene styrenated propenyl phenyl ether sulfate ammonium (manufactured by first Industrial pharmaceutical Co., Ltd. "AR-30") 1 part by weight
0.01 part by weight of an ethylene oxide/propylene oxide copolymer ("EP-10" manufactured by Ming Dynasty chemical industries Co., Ltd.)
Then, 0.08 parts by weight of t-butyl peroxyneodecanoate (tbutyl peroxyneo-caprate), 15 parts by weight of hydroxypropyl acrylate (HPA), and 85 parts by weight of cyclohexyl acrylate were added as a polymerization initiator to the polymerization vessel at 60 ℃, and polymerization was carried out for 6 hours to obtain a particulate (meth) acrylic polymer (9).
(meth) acrylic polymer (10): synthesis example 10
(Synthesis example 10)
To a reaction vessel were added 75 parts by weight of isobornyl acrylate, 20 parts by weight of cyclic trimethylolpropane formal acrylate (#200), 5 parts by weight of 4-hydroxybutyl acrylate (4HBA), and 50 parts by weight of ethyl acetate as a polymerization solvent, and the reaction vessel was heated to 65 ℃ while flowing nitrogen gas after bubbling with nitrogen gas. After heating for 30 minutes, 0.08 part by weight of a polymerization initiator solution prepared by diluting V-60(2, 2' -azobisisobutyronitrile, Wako pure chemical industries, Ltd.) as a polymerization initiator by 10 times with ethyl acetate was charged into a reaction vessel and subjected to a polymerization reaction for 5 hours to obtain a polymer solution. The solution was dried in an oven at 110 ℃ for 3 hours to obtain a (meth) acrylic polymer (10).
(meth) acrylic polymer (11): synthesis example 11
(Synthesis example 11)
Mixing the following components, coating with a spacer to obtain a thickness of 100 μm by sandwiching the PET sheet (50 μm manufactured by NIPPA) subjected to single-sided release treatment, and irradiating with chemical lamp (FL20SBL manufactured by Toshiba Co.) at an irradiation dose of 3000mJ/cm2The (meth) acrylic polymer (11) is obtained by irradiating ultraviolet rays.
65 parts by weight of isobornyl acrylate
25 parts by weight of Cyclic trimethylolpropane MethylalAcrylate (#200)
5 parts by weight of (2-methyl-2 ethyl-1, 3 dioxolan-4-yl) methacrylate (MEDOL-10)
5 parts by weight of 4-hydroxybutyl acrylate (4HBA)
IRGACURE 184 (manufactured by BASF corporation) 0.2 parts by weight
Polyvinyl acetate (X1): synthesis example X1
(Synthesis example X1)
A polymerization vessel made of glass and provided with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet was prepared. Into the polymerization vessel were charged 270 parts by weight of ion-exchanged water and 0.1 part by weight of partially saponified polyvinyl alcohol (PVA, number average molecular weight 11000, degree of saponification 88 mol%), followed by heating and stirring. Next, while the temperature in the polymerization vessel was set to 58 ℃, 0.08 parts by weight of lauroyl peroxide as a polymerization initiator and 100 parts by weight of a vinyl acetate monomer were added and polymerized for 6 hours to obtain polyvinyl acetate (X1) in the form of particles.
Polyvinyl acetate (X2): synthesis example X2
(Synthesis example X2)
A polymerization vessel made of glass and provided with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet was prepared. 250 parts by weight of vinyl acetate monomer and 3.8 parts by weight of methanol were charged into the polymerization vessel, and the inside of the polymerization vessel was purged with nitrogen while heating and stirring. Then, 0.02 part by weight of t-butyl peroxyneodecanoate as a polymerization initiator was added dropwise over 2.5 hours while setting the temperature in the polymerization vessel to 60 ℃, and after completion of the dropwise addition, polymerization was carried out for 2 hours to obtain a solution containing polyvinyl acetate (X2). The solution was dried in an oven at 110 ℃ for 3 hours to obtain polyvinyl acetate (X2).
Polyvinyl acetate (X3): synthesis example X3
(Synthesis example X3)
Polyvinyl acetate (X3) was obtained in the same manner as in synthesis example 1, except that 3-methyl-3-buten-1-ol (MB) was changed to Isopropylacrylamide (IPA) and the proportion of the structural unit derived from IPA was changed to 40 mol%.
Polyvinyl acetate (X4): synthesis example X4
(Synthesis example X4)
A polymerization vessel made of glass and provided with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet was prepared. Into the polymerization vessel were charged 270 parts by weight of ion-exchanged water and 0.1 part by weight of partially saponified polyvinyl alcohol (PVA, number average molecular weight 11000, degree of saponification 88 mol%), followed by heating and stirring. Next, while the temperature in the polymerization vessel was set to 58 ℃, 0.08 parts by weight of lauroyl peroxide, 100 parts by weight of a vinyl acetate monomer, and 20 parts by weight of 3-methyl-3-buten-1-ol (MB) as a polymerization initiator were added and polymerized for 6 hours to obtain particulate polyvinyl acetate (X4).
Polyvinyl acetal resin:
polyvinyl acetal resin (1) (PVB1,
Polyvinyl acetal resin (2) (PVB2, hydroxyl group content 34.5 mol%, butyralation degree 64.5 mol%,
(plasticizer)
D931 (bis (2-butoxyethyl) adipate)
3GO (triethylene glycol di-2-ethylhexanoate)
(Metal salt M)
Mg mixture (50: 50 (weight ratio) mixture of magnesium 2-ethylbutyrate and magnesium acetate)
(ultraviolet screening agent)
Tinuvin326(2- (2 '-hydroxy-3' -tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, "Tinuvin 326" from BASF)
(antioxidant)
BHT (2, 6-di-tert-butyl-p-cresol)
(example 1)
Preparation of the composition for forming layer 1:
the following mixed components were mixed and sufficiently kneaded by a mixing roll to obtain a composition for forming the
Polyvinyl acetate (1)100 parts by weight
Plasticizer (D931)70 parts by weight
An ultraviolet shielding agent (Tinuvin326) in an amount of 0.2% by weight in the obtained
An antioxidant (BHT) in an amount of 0.2 wt% in the obtained
Preparation of the compositions for forming the 2 nd and 3 rd layers:
the following mixed components were mixed and sufficiently kneaded by mixing rolls to obtain compositions for forming the 2 nd and 3 rd layers.
100 parts by weight of polyvinyl acetal resin (1) (PVB1,
Plasticizer (D931)35 parts by weight
The amount of Mg in the obtained 2 nd and 3 rd layers was 70ppm, and a metal salt M (Mg mixture)
An ultraviolet shielding agent (Tinuvin326) in an amount of 0.2% by weight in the obtained 2 nd and 3 rd layers
An antioxidant (BHT) in an amount of 0.2 wt% in the obtained 2 nd and 3 rd layers
Preparing an intermediate film:
the obtained composition for forming the 1 st layer and the obtained compositions for forming the 2 nd and 3 rd layers were extruded through a co-extruder to obtain an intermediate film having a structure of the 2 nd layer (thickness 370 μm)/the 1 st layer (thickness 100 μm)/the 3 rd layer (thickness 370 μm).
Preparing the laminated glass:
the resulting intermediate film was cut into a size of 30cm in length by 2.5cm in width. As the 1 st and 2 nd laminated glass members, transparent float glass having a thickness of 2.0mm, a length of 30mm and a width of 2.5cm in accordance with JIS R3202 was prepared. An interlayer film was interposed between 2 sheets of transparent float glass plates to obtain a laminate. The laminate was placed in a rubber bag, degassed at a vacuum degree of 2.6kPa for 20 minutes, moved to an oven in a degassed state, held at 90 ℃ for 30 minutes, vacuum-pressed, and pre-laminated. The laminated body subjected to the preliminary press bonding was pressed in an autoclave at 135 ℃ and a pressure of 1.2MPa for 20 minutes to obtain a laminated glass.
(examples 2 to 14 and comparative examples 1 to 4)
A laminated glass was obtained in the same manner as in example 1, except that the kinds of polyvinyl acetate, polyvinyl acetal resin, and plasticizer, and the mixing amounts thereof were changed as shown in tables 1 to 3 below.
(evaluation)
(1) Transparency (haze)
The obtained laminated glass was measured for haze based on jis k6714 using a haze meter ("TC-HIIIDPK" manufactured by tokyo electric color corporation). The haze value was judged as "O" when it was 0.5% or less, and was judged as "X" when it was more than 0.5%.
(2) Adhesion force
The composition for forming the 1 st layer was coated on a PET film (thickness: 70 μm) subjected to corona treatment to form a1 st layer having a thickness of 100 μm, to obtain a1 st laminate.
The compositions for forming the 2 nd and 3 rd layers were coated on a PET film (thickness: 100 μm) to form a2 nd layer having a thickness of 370 μm, to obtain a2 nd laminate.
The 1 st and 2 nd laminates thus obtained were cut into a size of 25mm and 80mm, respectively, and the 1 st and 2 nd layers were opposed to each other and subjected to plastic sealing at 110 ℃. Test samples of PET film/
The obtained test sample was subjected to a 180-degree peel test at 25 ℃ at a tensile rate of 300 mm/min using a tensile tester, and the adhesion between the 1 st layer and the 2 nd layer (also corresponding to the 3 rd layer) was evaluated.
(3) Bending test
Test samples obtained in the evaluation of the adhesive strength in (2) above were prepared. The test sample was folded in half at 180 degrees and restored, and whether or not the portion of the fold line was peeled off was evaluated. In comparative example 1, peeling of 1cm occurred, whereas in example 2, peeling did not occur.
(4) Sound insulation (first loss factor at 20 ℃ C.)
The laminated glass thus obtained was subjected to vibration by a vibration generator (vibration exciter G21-005D, manufactured by Shake Ltd.) used in the damping test. The vibration characteristics thus obtained were amplified by a mechanical impedance measuring apparatus ("XG-81" manufactured by RION), and the vibration spectrum was analyzed by an FFT spectrum Analyzer ("FFT Analyzer SA-
The details and results are shown in tables 1 to 3 below.
Description of the symbols
1
1a …
1b …
2
2a … outer side surface
3
3a … outer side surface
11,11A … intermediate film
11a …
11b … No. 2 surface
21 … part of 1 st laminated glass
22
31,31A … laminated glass
51 … roll
61 … core
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