WO2019069373A1 - Resin film to be used as interlayer of laminated glass, film material for interlayer of laminated glass, laminated glass and method for manufacturing laminated glass - Google Patents

Abstract

The present invention pertains to a resin film to be used as an interlayer of a laminated glass, wherein the maximum tanδ of the resin film within a frequency range of 100-100,000 Hz at 25°C is 0.5-4.0.

Description

Resin film used for interlayer film of laminated glass, film material for interlayer film of laminated glass, laminated glass, and method of manufacturing laminated glass

The present invention relates to a resin film used for an interlayer film of laminated glass, a film material for interlayer film of laminated glass, laminated glass, and a method of manufacturing laminated glass.

At present, laminated glass is widely used as glass for windows of vehicles such as automobiles, sunroofs, interior panels, etc., since it is safe that fragments of the glass are not scattered even if it is damaged due to external impact. . Laminated glass is also used in windows of trains, aircraft, construction machines, buildings and the like.

As an example of laminated glass, an interlayer film for laminated glass made of polyvinyl acetal resin such as polyvinyl butyral resin plasticized with a plasticizer is interposed between at least a pair of glass plates, and obtained by integrating them. (For example, see Patent Documents 1 to 3).

JP-A-62-100463 JP, 2005-206445, A International Publication No. 2012/091117

Most conventional laminated glass has the same level of fracture resistance as glass of the same thickness, but it is harder to break against an external impact and has high fracture resistance. Is required.

The present invention provides a resin film used for an interlayer film of laminated glass and a film material for an interlayer film of laminated glass which can produce laminated glass excellent in cracking resistance against an impact applied from the outside. The purpose is to Another object of the present invention is to provide a laminated glass excellent in impact resistance and cracking resistance and a method for producing the laminated glass using the resin film.

The present invention provides a resin film used for an interlayer film of laminated glass, which has a maximum value of tan δ at 25 ° C. and a frequency range of 100 to 100,000 Hz of 0.5 to 4.0.

The resin film may be formed from a resin composition containing a polymer of a monomer containing a (meth) acryloyl compound, and in that case, the weight average molecular weight of the polymer may be 200,000 to 2,000,000.

The (meth) acryloyl compound may contain an alkyl (meth) acrylate and a (meth) acrylate having a hydroxyl group. The content of the alkyl (meth) acrylate may be 50 to 95 parts by mass with respect to 100 parts by mass of the total amount of monomers.

The resin composition may further comprise a thermal crosslinking agent.

The resin film may have a haze of 10% or less.

The present invention also provides a film material for laminated film of laminated glass, comprising a base material and a resin layer provided on the base material, wherein the resin layer is a layer comprising the resin film according to the present invention described above. provide.

The present invention also provides a laminated glass comprising two opposing glass plates and an intermediate film sandwiched between two glass plates, wherein the intermediate film is the resin film according to the present invention described above. .

The present invention is further a method of producing laminated glass comprising two opposing glass plates and an intermediate film sandwiched between two glass plates, and the resin film according to the present invention described above, Producing laminated glass comprising the steps of bonding two glass plates to obtain a laminate, and heating and pressing the laminate under conditions of 30 to 150 ° C. and 0.3 to 1.5 MPa. Provide a way.

According to the present invention, it is possible to provide a resin film and a film material for an interlayer used as an interlayer of laminated glass capable of producing laminated glass having excellent split resistance against an impact applied from the outside. Can. The present invention can also provide a laminated glass excellent in impact resistance and cracking resistance and a method of producing laminated glass using the resin film.

It is a schematic cross section which shows one Embodiment of the film material for intermediate films of laminated glass. It is a schematic cross section which shows one embodiment of a laminated glass. It is a figure which shows the master curve created about the tan-delta value of the resin film of Example 2 and Comparative Example 3. FIG.

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings as the case may be. However, the present invention is not limited to the following embodiments.

<Definition>
In the present specification, a numerical range indicated by using “to” indicates a range including numerical values described before and after “to” as the minimum value and the maximum value, respectively. The upper limit or lower limit of the numerical range of one step may be replaced with the upper limit or lower limit of the numerical range of another step in the numerical range described stepwise in the present specification. In the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. “A or B” may contain either A or B, and may contain both. In the present specification, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless a plurality of substances corresponding to each component are present in the composition. means.

As used herein, "(meth) acrylate" means at least one of "acrylate" and the corresponding "methacrylate". The same applies to other similar expressions such as (meth) acryloyl.

<Resin film used for interlayer film of laminated glass>
The resin film used for the interlayer film of the laminated glass of the present embodiment has a maximum value of tan δ of 0.5 to 4.0 at a frequency of 100 to 100,000 Hz at 25 ° C. The resin film is used, for example, to form an intermediate film of laminated glass including two opposing glass plates and an intermediate film sandwiched between the two glass plates.

By forming an interlayer film of laminated glass using such a resin film, the interlayer film can dissipate energy due to the impact even when an impact is applied from the outside, and the high breakage resistance of the laminated glass Sex can be expressed.

More specifically, when the maximum value of tan δ is 0.5 or more, the energy dissipation due to impact is improved, and the break resistance of the laminated glass can be improved. From such a point of view, the maximum value of tan δ is preferably 0.7 or more, more preferably 0.8 or more, and still more preferably 1.0 or more. On the other hand, when the maximum value of tan δ is 4.0 or less, the amount of deformation of the laminated glass when an impact is applied can be suppressed by suppressing the plastic deformation, and the high split resistance of the laminated glass can be obtained. It can be improved. From such a viewpoint, the maximum value of the above-mentioned tan δ is preferably 3.0 or less, more preferably 2.0 or less, still more preferably 1.6 or less, and 1.4 or less. Being particularly preferred.

Here, the tan δ value can be calculated from a composite curve (master curve) obtained from the dynamic viscoelasticity measurement method and the time-temperature conversion rule. More specifically, for example, in accordance with the method according to JIS K 0129: 2005, first, using a dynamic viscoelasticity measuring instrument (TA Instruments Inc., product name “RSA-G2”), −70 to 100 The resin film is measured in a tensile measurement mode under the conditions of ° C., 0.05 / 0.5 / 5/50 Hz, and a strain amount of 1%. Next, from the obtained measurement results, a master curve is created at a reference temperature of 25 ° C. using the WLF method or the Arrhenius rule. Then, it is possible to read the maximum value of tan δ within the frequency range of 100 to 100000 Hz from the created master curve. Here, the frequency range of 100 to 100000 Hz means that one of two sheets of glass that forms a laminated glass by freely dropping a hard ball from a displacement height of several centimeters to one meter and several tens of centimeters. Is a frequency range selected on the assumption of the strain rate generated when a hard sphere collides with the glass of.

Hereafter, the specific means at the time of producing a master curve is demonstrated. First, from the measurement results of the dynamic viscoelasticity obtained above, the time-temperature conversion factor α _T is calculated for each temperature value by the following WLF equation or Arrhenius equation.

After that, from the value of the angular frequency ω at an arbitrary temperature T, the angular frequency ω ′ with respect to the reference temperature T ₀ can be calculated by the following equation A, and the relationship between the angular frequency ω ′ and the measured dynamic viscoelasticity is By drawing, it is possible to obtain a master curve in which the horizontal axis is changed to frequency.
α _T = ω '/ ω (A)
The series of calculations described above can be calculated using TRIOS Software (TA Instruments, product name) attached to “RSA-G2”.

(Resin composition)
The resin film according to the present embodiment can be formed from a resin composition. The composition of the resin composition is not particularly limited as long as the maximum value of the above-mentioned tan δ in the resin film is within the desired range. The resin composition may contain, for example, a polymer having rubber elasticity.

(Polymer)
Examples of the polymer having rubber elasticity include urethane polymers, styrene polymers, acrylic polymers, vinyl chloride polymers, amide polymers, and olefin polymers. These polymers may be used alone or in combination of two or more. Among them, at least one selected from the group consisting of a urethane-based polymer, a styrene-based polymer, and an acrylic-based polymer, from the viewpoint of being able to adjust the maximum value of the above-mentioned tan δ in the resin film more efficiently into a desired range. It is preferable to contain a seed, and it is more preferable to contain an acrylic polymer.

The polymer contained in the resin composition may be a polymer of a monomer containing a (meth) acryloyl compound, that is, a polymer having a structural unit derived from the (meth) acryloyl compound. The (meth) acryloyl compound means a compound having a (meth) acryloyl group in the molecule, preferably a compound having one (meth) acryloyl group in the molecule. However, in the present specification, the (meth) acryloyl compound does not include the one corresponding to a silicon compound having an ethylenically unsaturated group described later.

Examples of (meth) acryloyl compounds include (meth) acrylic acid, (meth) acrylamide, (meth) acrylamide derivatives, alkyl (meth) acrylates having a linear or branched alkyl group, and alkylene glycol chains ( Meta) Acrylate, (Meth) acrylate having hydroxyl group, (Meth) acrylate having aromatic ring, (meth) acrylate having alicyclic group, (meth) acryloyl morpholine, tetrahydrofurfuryl (meth) acrylate and having isocyanate group (Meth) acrylate is mentioned.

Examples of alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) Acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate and stearyl (meth) acrylate And alkyl (meth) acrylates having an alkyl group having 1 to 18 carbon atoms. Among them, as the alkyl (meth) acrylate, n-butyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-octyl (meth) acrylate are preferable, and 2-ethylhexyl (meth) acrylate is preferable. More preferable. Also, alkyl acrylates are preferred to alkyl methacrylates. The alkyl (meth) acrylates may be used alone or in combination of two or more.

As the (meth) acrylate having a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1- There may be mentioned hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 1-hydroxybutyl (meth) acrylate.

Examples of (meth) acrylates having an alkylene glycol chain include polyethylenes such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate and hexaethylene glycol mono (meth) acrylate. Glycol mono (meth) acrylate; Polypropylene glycol mono (meth) acrylate such as dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate; Dibutylene glycol mono (meth) Polybutylene glycol mono (meth) acrylates such as acrylate and tributylene glycol mono (meth) acrylate; methoxy Triethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxyhexaethylene glycol (meth) acrylate, methoxyoctaethylene glycol (meth) acrylate, methoxynona ethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) Alkoxy polyalkylene glycol (meth) acrylates such as acrylate, methoxy hepta propylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, butoxy ethylene glycol (meth) acrylate, butoxy diethylene glycol (meth) acrylate and the like can be mentioned. In addition, these alkylene glycol chain-containing (meth) acrylates may be used alone or in combination of two or more.

Examples of aromatic ring-containing (meth) acrylates include benzyl (meth) acrylate and phenoxyethyl (meth) acrylate. Examples of (meth) acrylates having an alicyclic group include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate. Examples of (meth) acrylamide derivatives include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) Acrylamide, N, N-diethyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide are included. Examples of (meth) acrylates having an isocyanate group include 2- (2-methacryloyloxyethyloxy) ethyl isocyanate and 2- (meth) acryloyloxyethyl isocyanate.

The polymer according to the present embodiment preferably contains a structural unit derived from an alkyl (meth) acrylate. The polymerization ratio of the alkyl (meth) acrylate is preferably 50 to 95% by mass, more preferably 50 to 90% by mass, and 50 to 85% by mass with respect to the total mass of the polymer. Is more preferred. Since the adhesiveness of a resin layer and a to-be-adhered body can be improved as the polymerization ratio of an alkyl (meth) acrylate is such a range, the break resistance of laminated glass can be improved more. Such a polymer can be obtained by polymerizing a monomer containing an alkyl (meth) acrylate in the same content ratio as the above-mentioned polymerization ratio.

It is preferable that the polymer which concerns on this embodiment contains the structural unit derived from the (meth) acrylate which has a hydroxyl group. The polymerization ratio of the (meth) acrylate having a hydroxyl group is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and more preferably 10 to 30% by mass with respect to the total mass of the polymer. It is further preferred that When the polymerization ratio of the (meth) acrylate having a hydroxyl group is in such a range, the break resistance of the laminated glass can be further improved, and the transparency of the obtained resin film can be improved.

Transparency can use haze as an index. The haze is a value (%) representing the turbidity, which is given by the total transmittance T _t of the light emitted by the lamp and dropped in the sample and the transmittance T _{d of the} light diffused and scattered in the sample ((t It is calculated as T _d / T _t ) × 100. These are defined by JIS K 7136, and can be measured by a commercially available turbidity meter, for example, Nippon Denshoku Kogyo Co., Ltd., product name “NDH-5000”.

The (meth) acryloyl compound according to the present embodiment preferably contains an alkyl (meth) acrylate and a (meth) acrylate having a hydroxyl group from the viewpoint of improving the transparency of the laminated glass. In this case, the content of the alkyl (meth) acrylate may be 50 to 95 parts by mass, may be 50 to 90 parts by mass, and is 50 to 85 parts by mass with respect to 100 parts by mass of the total amount of monomers. Good. The content of the (meth) acrylate having a hydroxyl group may be 5 to 40 parts by mass, and may be 10 to 30 parts by mass with respect to 100 parts by mass of the total amount of monomers.

The (meth) acryloyl compound further contains a compound having a (meth) acryloyl group and a polar group such as a morpholino group, an amino group, a carboxyl group, a cyano group, a carbonyl group, a nitro group or a group derived from an alkylene glycol group. You may By containing the (meth) acrylate having a polar group, the adhesion between the resin layer and the adherend can be improved.

The monomer which concerns on this embodiment may also contain the silicon compound which has an ethylenically unsaturated group other than the said (meth) acryloyl compound. As a silicon compound having an ethylenically unsaturated group, it has a group having an unsaturated bond such as (meth) acryloyl group, styryl group, cinnamic acid ester group, vinyl group or allyl group, and silicon as a constituent atom It is not particularly limited as long as it is a compound having The silicon compound according to the present embodiment may be a siloxane compound or a silane compound, and for example, the compounds represented by the formulas (a), (b) or (c) are used alone or in combination of two or more. May be

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a methyl group, and R ⁸ represents monovalent carbon L ¹ represents a hydrogen group, L ¹ represents a divalent hydrocarbon group or a single bond which may be interrupted by an oxygen atom, and m represents an integer of 1 to 300.

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a methyl group, and L ¹ and L ² each represent It independently represents a divalent hydrocarbon group or a single bond which may be intervened by an oxygen atom, and n represents an integer of 1 to 300.

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a monovalent hydrocarbon group, and L ³ may be an oxygen atom 2 Represents a valent hydrocarbon group or a single bond.

Examples of the monovalent hydrocarbon group include an alkyl group having 1 to 6 carbon atoms and a phenyl group. Examples of the divalent hydrocarbon group include an alkylene group having 1 to 20 carbon atoms.

In the polymer according to this embodiment, the polymerization ratio of the monomer unit derived from the silicon compound is preferably 2 to 20% by mass, and preferably 4 to 10% by mass, with respect to the total mass of the polymer. More preferable. When the polymerization ratio of the silicon compound is in such a range, the adhesion between the resin film and the adherend is improved, and the toughness of the laminate is improved, thereby further improving the split resistance of the laminated glass. be able to.

The monomer may contain a compound having two or more (meth) acryloyl groups or a compound having a polymerizable group other than the (meth) acryloyl group, as long as the effects of the present invention are not impaired. As a compound which has polymeric groups other than a (meth) acryloyl group, an acrylonitrile, styrene, vinyl acetate, ethylene, propylene, and divinylbenzene are mentioned, for example.

The weight-average molecular weight (Mw) of the polymer is preferably 200,000 to 2,000,000, preferably 500,000 to 1,500,000, as determined by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. It is more preferable, and more preferably 600000 to 1300000. When the Mw of the polymer is 200,000 or more, the adhesion to the adherend is improved, so that the split resistance of the laminated glass is further improved, and when it is 2,000,000 or less, the viscosity of the resin composition is high. In addition, the processability at the time of forming the resin film becomes good, and as a result, the split resistance of the laminated glass is further improved.

The polymer according to the present embodiment can be synthesized, for example, using a known polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and the like.

As a polymerization initiator at the time of synthesizing a polymer, a compound which generates a radical by heat can be used. Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide and lauroyl peroxide; 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and the like Azo compounds may be mentioned.

(Other additives)
The resin composition may, if necessary, contain various additives together with the above-mentioned polymer.

As the additive, for example, a crosslinking agent may be used to increase the cohesion of the resin composition. Specific examples of the crosslinking agent include photocrosslinking agents and thermal crosslinking agents.

As the photocrosslinking agent, for example, an alkylene diol di (meth) acrylate having an alkylene group having 1 to 20 carbon atoms; an alkylene glycol di (meth) acrylate such as polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate Bisphenol type di (meth) acrylates such as ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, bisphenol A type epoxy (meth) acrylate; and urethane di (meth) acrylates having a urethane bond It can be mentioned.

The urethane di (meth) acrylate having a urethane bond may have a polyalkylene glycol chain from the viewpoint of good compatibility with other components, and from the viewpoint of securing transparency, it has an alicyclic structure. You may have. If the compatibility between the photocrosslinking agent and the polymer is high, clouding of the resin film formed from the resin composition tends to be easily suppressed.

The weight average molecular weight of the photocrosslinking agent is preferably 100,000 or less, more preferably 300 to 100,000, and more preferably 500 to 80,000 from the viewpoint of being able to further suppress the generation of air bubbles and peeling under high temperature or high temperature and high humidity. It is further preferred that

The content ratio in the case of using a photocrosslinking agent is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 7% by mass or less based on the total mass of the polymer. preferable. A resin film which has sufficient adhesiveness can be obtained as it is such a range. The lower limit of the content of the photocrosslinking agent is not particularly limited, but is preferably 0.1% by mass or more, more preferably 2% by mass or more, from the viewpoint of making the film forming property favorable. It is more preferable that the content is at least% by mass.

As a thermal crosslinking agent, thermal crosslinking agents, such as an isocyanate compound, a melamine compound, an epoxy compound, can be used, for example. As the thermal crosslinking agent, a trifunctional or tetrafunctional polyfunctional thermal crosslinking agent is more preferable from the viewpoint of forming a gradually spread network structure in the resin film and appropriately adjusting the flexibility of the resin film.

From the viewpoint of reactivity, an isocyanate compound is preferable as the thermal crosslinking agent, and a polyisocyanate compound is more preferable. Examples of the polyisocyanate compound include a trimer of hexamethylene diisocyanate, a triol such as trimethylolpropane, a polyfunctional hexamethylene diisocyanate compound which is a reaction product of a diol or a monofunctional alcohol and hexamethylene diisocyanate. .

The content ratio in the case of using a thermal crosslinking agent is preferably 5% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less based on the total mass of the polymer. preferable. A resin film which has sufficient adhesiveness can be obtained as it is such a range. The lower limit of the content of the thermal crosslinking agent is not particularly limited, but is preferably 0.01% by mass or more from the viewpoint of improving the film formability.

When either the polymer or the crosslinking agent is an active energy curing system, a photopolymerization initiator may be included. The photopolymerization initiator promotes the curing reaction by irradiation of active energy rays. Active energy rays refer to ultraviolet rays, electron beams, α rays, β rays, γ rays and the like.

The photopolymerization initiator is not particularly limited, and it is possible to use known materials such as benzophenone compounds, anthraquinone compounds, benzoyl compounds, sulfonium salts, diazonium salts, onium salts and the like.

As a photopolymerization initiator, for example, benzophenone, N, N, N ', N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N, N', N'-tetraethyl-4,4 ' -Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, α-hydroxyisobutylphenone, 2-ethylanthraquinone, t-butylanthraquinone, 1,4-dimethylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 1,2-benzoanthraquinone, 2-phenylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2, 2 Aromatic ketone compounds such as dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-diethoxyacetophenone; benzoin, methylbenzoin, ethyl Benzoin compounds such as benzoin; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin phenyl ether; benzyl compounds such as benzyl, benzyl dimethyl ketal; β- (acridin-9-yl) (meth) acrylic Ester compounds such as acids; 9-phenylacridine, 9-pyridylacridine, acridine compounds such as 1,7-diaclidinoheptane; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- ( o-k Rophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) 5-phenylimidazole dimer, 2- (2, 2,4,5-Triarylimidazole dimers such as 4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone; 2-methyl-1- [4- (methylthio) phenyl] -2 Morpholino-1-propane; bis (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide; oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) . These compounds may be used in combination of two or more.

As a photopolymerization initiator, from the viewpoint of not coloring the resin composition, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2) Α-hydroxyalkylphenone compounds such as -hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one; bis (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide, Acyl phosphine oxide compounds such as 2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentyl phosphine oxide, 2,4,6-trimethyl benzoyl-diphenyl phosphine oxide; oligo (2-hydroxy-2-methyl-1) -(4- (1-Methylvinyl) phenyl) propanone And the like.

The photopolymerization initiator is, for example, bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide, bis (2,6-dimethoxy benzoyl) -2,4,4- from the viewpoint of particularly forming a thick resin film. Acyl phosphine oxide compounds such as trimethyl-pentyl phosphine oxide and 2,4,6-trimethyl benzoyl diphenyl phosphine oxide may be included.

The content ratio of the photopolymerization initiator is preferably 0.05 to 5% by mass, and more preferably 0.1 to 3% by mass, with respect to the total mass of the resin composition. % By mass is more preferred. By setting the content ratio of the photopolymerization initiator to 5% by mass or less, the transmittance tends to be high, and the hue is not likely to be yellowish, and a resin film having excellent transparency tends to be easily obtained.

The resin composition may optionally contain an additive other than the crosslinking agent. As the additive, for example, a polymerization inhibitor such as paramethoxyphenol added for the purpose of enhancing the storage stability of the resin composition, or for the purpose of enhancing the heat resistance of the interlayer obtained by photocuring the resin composition. An antioxidant such as triphenyl phosphite, a light stabilizer such as HALS (Hindered Amine Light Stabilizer) added for the purpose of enhancing the resistance of the resin composition to light such as ultraviolet light, and an adhesive property of the resin composition to glass And silane coupling agents to be added.

The resin composition may contain an inorganic filler, for example, crushed silica, fused silica, mica, clay mineral, short glass fiber or fine powder, hollow glass, calcium carbonate, quartz powder, metal hydrate Etc. The content of the inorganic filler is preferably 0.01 to 100 parts by mass, more preferably 0.05 to 50 parts by mass, and more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin composition on the basis of the total solid content. Parts are more preferred. When the content of the inorganic filler is 0.01 to 100 parts by mass, sufficient low shrinkage, improvement in mechanical strength, low coefficient of thermal expansion and the like can be obtained. The dispersibility of the inorganic filler may be improved by treatment with a commercially available surface treatment agent such as a coupling agent, or treatment with a triple roll, bead mill, or a disperser such as a nanomizer.

<Interlayer film film material for laminated glass>
The film material for an intermediate film of the laminated glass of the present embodiment has a substrate and a resin layer provided on the substrate. A resin layer is a layer which consists of a resin film concerning this embodiment mentioned above.

FIG. 1 is a schematic cross-sectional view showing an embodiment of an intermediate film film material of laminated glass. As shown in FIG. 1, the film material 1 for an intermediate film of the present embodiment includes a resin layer 11 and one base 10 and the other base 12 laminated so as to sandwich the resin layer 11. May be

As the substrate 10, it is preferable to use a substrate which is lightly releasable than the substrate 12. As the base material 10, polymer films, such as a polyethylene terephthalate, a polypropylene, polyethylene, are mentioned, for example, Especially, a polyethylene terephthalate film (Hereinafter, it may be mentioned "PET film") is preferable. The thickness of the substrate 10 is preferably 25 to 150 μm, more preferably 30 to 100 μm, and still more preferably 40 to 80 μm from the viewpoint of workability.

The planar shape of the substrate 10 is preferably larger than the planar shape of the resin layer 11, and the outer edge of the substrate 10 preferably protrudes outward beyond the outer edge of the resin layer 11. The width of the outer edge of the base 10 overhanging the outer edge of the resin layer 11 is preferably 2 to 20 mm, and is preferably 4 to 10 mm, from the viewpoint of ease of handling, ease of peeling, and reduction of adhesion of dust and the like. It is more preferable that When the planar shape of the resin layer 11 and the base material 10 is a substantially rectangular shape such as a substantially rectangular shape, the width of the outer edge of the base material 10 overhangs the outer edge of the resin layer 11 is 2 to 20 mm in at least one side. It is preferably 4 to 10 mm on at least one side, more preferably 2 to 20 mm on all sides, and particularly preferably 4 to 10 mm on all sides.

As the substrate 12, it is preferable to use a substrate that is heavier releasable than the substrate 10. Examples of the substrate 12 include polymer films such as polyethylene terephthalate (PET), polypropylene, and polyethylene. Among them, PET films are preferable. The thickness of the substrate 12 is preferably 50 to 200 μm, more preferably 60 to 150 μm, and still more preferably 70 to 130 μm from the viewpoint of workability.

The planar shape of the substrate 12 is preferably larger than the planar shape of the resin layer 11, and the outer edge of the substrate 12 preferably protrudes outward beyond the outer edge of the resin layer 11. The width of the outer edge of the base 12 protruding beyond the outer edge of the resin layer 11 is preferably 2 to 20 mm, more preferably 4 to 10 mm, from the viewpoint of ease of handling, ease of peeling, and reduction of adhesion of dust and the like. It is more preferable that When the planar shape of the resin layer 11 and the base 12 is a substantially rectangular shape such as a substantially rectangular shape, the outer edge of the base 12 protrudes more than the outer edge of the resin layer 11 by 2 to 20 mm in at least one side. It is preferably 4 to 10 mm on at least one side, more preferably 2 to 20 mm on all sides, and particularly preferably 4 to 10 mm on all sides.

The peel strength between the base 10 and the resin layer 11 is preferably lower than the peel strength between the base 12 and the resin layer 11. As a result, the base 12 becomes more difficult to peel from the resin layer 11 than the base 10. The peel strength can be adjusted, for example, by subjecting the substrate 12 and the substrate 10 to a surface treatment. As the surface treatment method, for example, release treatment of the substrate with a silicone compound or a fluorine compound is mentioned.

A known technique can be used as a method of forming the resin layer 11. For example, first, the resin composition according to the present embodiment is diluted with a volatile solvent such as 2-butanone, cyclohexanone, methyl ethyl ketone, ethyl acetate, toluene or the like to prepare a coating liquid. Next, the coating solution is applied onto the substrate 12 and the solvent is removed by drying to form a resin layer having an arbitrary thickness. In the preparation of the coating solution, each component may be blended and then diluted with a solvent, or may be previously diluted with a solvent prior to blending each component. As a coating method, for example, known methods such as a flow coating method, a roll coating method, a gravure coating method, a wire bar coating method, and a lip die coating method can be used.

After forming the resin layer 11 on the substrate 12, the substrate 10 is laminated on the resin layer 11 to produce a film material for an intermediate film according to the present embodiment. The resin layer 11 is configured to be sandwiched between the base 10 and the base 12. In order to control the releasability between the resin layer 11 and the base material 10 and the base material 12, even if the resin composition contains a surfactant such as a polydimethylsiloxane surfactant or a fluorine surfactant. Good.

The thickness of the resin layer 11 is not particularly limited because it is appropriately adjusted depending on the use and method, but may be 10 to 5000 μm, 25 to 200 μm, 25 to 180 μm, or 25 to 150 μm. When used in this range, it is possible to obtain an interlayer for laminated glass which is further excellent in split resistance against an externally applied impact.

The light transmittance of the resin layer 11 to light in the visible light range (wavelength: 380 nm to 780 nm) is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more .

The haze of the resin layer 11 is preferably 10% or less, more preferably 5% or less, still more preferably 3% or less, and particularly preferably 1% or less. When the haze of the resin layer 11 is 10% or less, appearance defects such as environmental foreign matter mixed in the manufacturing process of the film material for interlayer and laminated glass can be easily detected, and sufficient visibility as laminated glass is secured. can do.

According to the film material 1 for interlayers which concerns on this embodiment, storage and conveyance can be made easy, without damaging the resin layer 11. FIG.

The resin layer 11 can bond, for example, glass, a transparent substrate (or transparent film) made of glass and resin, or transparent substrates (or transparent film) made of resin as an intermediate film.

<Laminated glass>
The intermediate film of laminated glass according to the present embodiment (hereinafter, sometimes simply referred to as “intermediate film”) can be applied to various kinds of laminated glass. The laminated glass includes two opposing glass plates and an intermediate film sandwiched between the two glass plates, and the intermediate film is a film made of the resin film according to the present embodiment. The method for producing a laminated glass according to the present embodiment includes the steps of bonding two glass plates via the above-described resin film to obtain a laminate, and conditions of 30 to 150 ° C. and 0.3 to 1.5 MPa. Heating and pressing the laminate.

Examples of the glass include float glass, air-cooled tempered glass, chemically tempered glass and double-layered glass.

The thickness of the glass may be, for example, 0.1 to 50 mm, 0.5 to 30 mm, 1 to 20 mm, or 2 to 10 mm.

FIG. 2 is a side sectional view schematically showing an embodiment of the laminated glass. In the laminated glass 2 shown in FIG. 2, a float glass 20, an intermediate film 21 and a float glass 22 are laminated in this order. The laminated glass 2 shown in FIG. 2 can be manufactured, for example, by the following method.

First, the base material 10 in the film material 1 for intermediate films is peeled from the resin layer 11 to expose the surface of the resin layer 11. Next, the surface of the resin layer 11 to be the intermediate film 21 is attached to the first adherend float glass 20 and pressed by a roller or the like, and then the substrate 12 is peeled off from the resin layer 11 to expose the surface. . Subsequently, the surface of the resin layer 11 is attached to the float glass 22 as a second adherend, heat and pressure treatment (autoclave treatment) is performed, and the float glass 20 and the interlayer film 21 (resin layer 11) are interposed. The laminated glass 2 which bonded together 21 is produced.

By using the resin layer 11, adherends can be easily bonded without wrinkles. The heat and pressure treatment can also be performed at a low temperature and in a short time. By using the resin layer 11, stable transparency of the laminated glass 2 can be maintained without the intermediate film 21 being whitened.

The conditions of the heat and pressure treatment are a temperature of 30 to 150 ° C. and a pressure of 0.3 to 1.5 MPa, but from the viewpoint of being able to further remove entrapped air bubbles, it is 0.3 to 0 at 50 to 70 ° C. It may be 0.5 MPa. The treatment time is preferably 5 to 60 minutes, and more preferably 10 to 30 minutes.

Although glass is used as the second adherend in the above description, the second adherend may be a transparent substrate made of resin. As a transparent substrate, transparent plastic substrates, such as an acrylic resin substrate, a polycarbonate substrate, a cycloolefin polymer substrate, a polyester substrate, are mentioned, for example.

The interlayer film according to the present embodiment is attached by combining a laminated glass with a functional layer having functionality such as an antireflective layer, an antifouling layer, a dye layer, a hard coat layer, a sound insulation layer, a heat shield layer or other resin layers. You may use it to match. That is, in the intermediate film according to the present embodiment, the resin layer may have a single layer structure of one layer, or may have a multilayer structure in which two or more layers are laminated.

The antireflection layer may be a layer having an antireflection property such that the visible light reflectance is 5% or less. As the antireflective layer, a layer obtained by treating a transparent substrate such as a transparent plastic film by a known antireflective method can be used.

The antifouling layer is for making it difficult for the surface to be contaminated. As the antifouling layer, a known layer composed of a fluorine-based resin, a silicone-based resin or the like can be used to lower the surface tension.

The dye layer is used to increase color purity, and is used to reduce light of unnecessary wavelengths transmitted through the laminated glass. The dye layer can be obtained by dissolving a dye that absorbs light of unnecessary wavelength in a resin, and forming or laminating it on a base film such as a polyethylene film or a polyester film.

The hard coat layer is used to increase the surface hardness. As the hard coat layer, for example, an acrylic resin such as urethane acrylate and epoxy acrylate; a film obtained by forming an epoxy resin or the like on a base film such as a polyethylene film or the like can be used. Similarly, in order to increase the surface hardness, a hard coat layer formed or laminated on a transparent protective plate of glass, acrylic resin, polycarbonate or the like can also be used.

The sound insulation layer may be any known film layer as long as it has a function of controlling the loss coefficient (dB) when sound having a frequency of 100 to 10000 Hz passes through the laminated glass.

The heat shielding layer may have any function to absorb or reflect light in the infrared region (wavelength 780 nm or more), and known film layers can be used.

The other resin layer is not particularly limited as long as the effects of the present invention are not impaired. As resin used for such a resin layer, polyvinyl acetal resin, such as polyvinyl butyral resin, ethyl vinyl alcohol resin, an ionomer, etc. are mentioned.

When setting it as such a laminated body, the resin layer 11 can be laminated | stacked using a roll lamination, a vacuum bonding machine, or a sheet-fee bonding machine.

By the method for producing laminated glass according to the present embodiment, it is possible to produce laminated glass having excellent split resistance against an impact applied from the outside.

Hereinafter, the present invention will be described by way of examples. However, the present invention is not limited to the following examples.

The weight average molecular weight (Mw) of the polymer produced in the production example was measured according to the GPC method using a calibration curve with standard polystyrene and using the following GPC measurement apparatus and measurement conditions.

RI Detector: L-3350 (Hitachi High-Tech Science, Product Name)
Eluent: THF
Column: Gelpac GL-R420 + R430 + R440 (product name of Hitachi Chemical Co., Ltd.)
Column temperature: 40 ° C
Flow rate: 2.0 mL / min

<Preparation of polymer>
Production Example 1
Add 80.0 g of 2-ethylhexyl acrylate, 20.0 g of 2-hydroxyethyl acrylate and 145.0 g of ethyl acetate to a reaction vessel equipped with a condenser, thermometer, stirrer, dropping funnel and nitrogen inlet, and add 100 mL / min. It heated from normal temperature (25 degreeC) to 65 degreeC for 15 minutes, substituting nitrogen by the airflow volume. Thereafter, while maintaining the temperature at 65 ° C., a solution of 0.1 g of lauroyl peroxide in 5.0 g of ethyl acetate is added and reacted for 8 hours to obtain a solution of 40% solid content concentration of polymer A-1 (Mw 900000) Obtained.

Production Example 2
The solid content concentration is the same as in Production Example 1 except that 80.0 g of 2-ethylhexyl acrylate, 10.0 g of 2-hydroxyethyl acrylate, 10.0 g of acryloyl morpholine and 145.0 g of ethyl acetate are added to a reaction vessel A solution of 40% of polymer A-2 (Mw 700000) was obtained.

Production Example 3
Same as Production Example 1 except that 80.0 g of 2-ethylhexyl acrylate, 15.0 g of 2-hydroxyethyl acrylate, 5.0 g of one end methacryloyl-modified polysiloxane compound (Mw 12000) and 145.0 g of ethyl acetate were added to a reaction vessel A solution of polymer A-3 (Mw 850000) having a solid content concentration of 40% was obtained.

Production Example 4
A polymer A having a solid content concentration of 40% is operated in the same manner as in Production Example 1 except that 80.0 g of n-butyl acrylate, 20.0 g of 4-hydroxybutyl acrylate and 145.0 g of ethyl acetate are added to a reaction vessel. A solution of -4 (Mw 1250000) was obtained.

Production Example 5
90.0 g of 2-ethylhexyl acrylate, 10.0 g of 2-hydroxyethyl acrylate and 145.0 g of ethyl acetate were added to a reaction vessel, and the reaction was carried out in the same manner as in Production Example 1 except that the reaction time was 6 hours. A solution of polymer A-5 (Mw 100000) having a concentration of 40% was obtained.

Production Example 6
78.5 g of n-butyl acrylate, 19.5 g of 2-ethylhexyl acrylate, 2.0 g of acrylic acid and 100.0 g of ultrapure water in a reaction vessel equipped with a condenser, thermometer, stirrer, dropping funnel and nitrogen inlet pipe And 1.0 g of polyvinyl alcohol as a stabilizer, and heated from normal temperature (25.degree. C.) to 65.degree. C. for 15 minutes while performing nitrogen substitution with a flow rate of 100 ml / min. Thereafter, while maintaining at 65 ° C., 0.1 g of t-butylperoxy-2-ethylhexanoate is charged, reacted for 6 hours, and water is distilled off to obtain a polymer A-6 (Mw: 2200000). The

<Preparation of film material for interlayer film of laminated glass>
Example 1
To 100 parts by mass of the polymer of solution A-1 obtained in Production Example 1, 0.2 part by mass of polyisocyanate compound (Tosoh Corp., product name “Coronato HL”) is mixed as a thermal crosslinking agent, A coating solution of the resin composition was prepared.

Next, a coating liquid of the above resin composition is coated on a 75 μm-thick PET film (base 12) that has been subjected to a release treatment using a bar coater so that the thickness after drying is 100 μm. It heat-dried for 10 minutes, and formed the resin layer (resin film). Thereafter, a 75 μm-thick release-treated PET film (base material 10) was covered on the resin layer and attached with a 1.0 kgf hand roller to prepare an interlayer film material of laminated glass.

Example 2
A coating solution and a film material of a resin composition were obtained in the same manner as in Example 1 except that the solution of the polymer A-2 obtained in Production Example 2 was used.

Example 3
The same procedure as in Example 1 is repeated except that the solution of polymer A-3 obtained in Production Example 3 is applied twice so that the thickness after drying is 200 μm, and the total thickness is 400 μm. The coating liquid and film material of the resin composition were obtained.

Example 4
A coating solution and a film material of a resin composition were obtained in the same manner as in Example 1 except that the solution of the polymer A-4 obtained in Production Example 4 was used.

Comparative Example 1
The same procedure as in Example 1 is repeated except that the solution of the polymer A-5 obtained in Production Example 5 is applied twice so that the thickness after drying is 200 μm, and the total thickness is 400 μm. The coating liquid and film material of the resin composition were obtained.

Comparative example 2
A coating solution and a film material of a resin composition were obtained in the same manner as in Example 1 except that the solution of the polymer A-6 obtained in Production Example 6 was used.

Comparative example 3
Polyvinyl butyral resin (the degree of acetalization 68.0 mol%, the proportion of vinyl acetate component 0.6 mol%) of which the half width of the peak corresponding to a hydroxyl group obtained when the infrared absorption spectrum is measured is 245 cm ^-1 A part by mass and 38 parts by mass of triethylene glycol di-2-ethylhexanoate as a plasticizer are mixed, sufficiently melt-kneaded with a mixing roll, and press-molded for 30 minutes at 150 ° C. with a press molding machine, A resin film having a thickness of 380 μm was obtained, and this was used as an intermediate film for glass.

<Evaluation of resin film>
The resin films obtained in the respective examples and comparative examples were evaluated by the following method. The results are shown in Table 1.

1. Measurement of Maximum Tan δ Value The film material for an intermediate film obtained in Examples 1 to 4 and Comparative Examples 1 and 2 is cut out to a size of 10 mm × 40 mm, and the base material 10 and the base material 12 are peeled off to measure tan δ value. A sample (resin film) was obtained. Moreover, in the comparative example 3, the resin film was cut out to the size of 10 mm x 40 mm, and the sample for tan-delta value measurement was obtained.

The obtained sample is set in a dynamic viscoelasticity measuring instrument (TA Instruments Inc., product name “RSA-G2”) so that the measurement length is 20 mm, −70 to 100 ° C., 0.05 The measurement was performed in a tensile measurement mode under a condition of 1 / 0.5 / 5/50 Hz and a strain amount of 1%. Next, from the obtained measurement results, a master curve was created with a reference temperature of 25 ° C. using Arrhenius law, and the maximum value of tan δ in a frequency range of 100 to 100,000 Hz was read from the obtained master curve . In addition, preparation of a master curve was calculated using TRIOS Software (TA instrument, product name) attached to "RSA-G2." The master curve created about the tan-delta value of the resin film of Example 2 and the comparative example 3 in FIG. 3 is shown.

2. Measurement of haze The film material for an intermediate film of Examples 1 to 4 and Comparative Examples 1 to 2 was cut out to a size of 50 mm × 50 mm, the base material 10 was peeled off, and one surface of the resin layer was exposed and then exposed. A double-sided tape was attached to the frame portion of the resin layer, and set via a double-sided tape at the measurement site of a turbidity meter (Nippon Denshoku Kogyo Co., Ltd., product name "NDH-5000"). Next, the base 12 was peeled off from the resin layer to expose the other surface of the resin layer, and the haze of the resin layer was measured. Further, in Comparative Example 3, the resin film is cut out to a size of 50 mm × 50 mm, a double-sided tape is attached to the frame, and set at the measurement site of a turbidimeter (Nippon Denshoku Kogyo Co., Ltd., product name “NDH-5000”) Then the haze was measured.

<Production of laminated glass>
In Examples 1 to 4 and Comparative Examples 1 to 2, after the substrate 10 is peeled off from the produced film material for an intermediate film to expose the surface of the resin layer, the surface of the resin layer is 110 mm long, 110 mm wide, and thickness It stuck on a 2.7 mm float glass, and pressed with the roller. Next, the substrate 12 is peeled off from the resin layer to expose the surface of the resin layer, and the surface of the resin layer is attached to float glass 110 mm long, 110 mm wide, and 2.7 mm thick using a vacuum laminating machine in a vacuum state Then, a laminate was prepared. Thereafter, the laminate was subjected to heat and pressure treatment using an autoclave under the conditions of a temperature of 50 ° C. and a pressure of 0.5 MPa for 30 minutes to obtain a laminated glass.

Further, in Comparative Example 3, the resin film was sandwiched with float glass and autoclaved under conditions of temperature 135 ° C., pressure 115 N / cm ² MPa, and holding for 60 minutes to obtain laminated glass.

<Evaluation of laminated glass>
The laminated glass obtained in each Example and Comparative Example was evaluated by the following method. The results are shown in Table 1.

3. Impact resistance test A steel ball with a mass of 1040 g and a diameter of 63.5 mm at a position within 25 mm of the 110 mm long and 110 mm wide, supported peripheral laminated glass, height 5 cm in steps from 5 cm in height Were raised sequentially and dropped, and the height at which the glass broke was recorded. Six sheets of each laminated glass were tested, the average height was calculated, and the laminated glass which showed the value of 50 cm or more was made into the laminated glass with high fracture resistance.

DESCRIPTION OF SYMBOLS 1 ... Film material for intermediate films, 2 ... Laminated glass, 10, 12 ... Base material, 11 ... Resin layer, 20, 22 ... Float glass, 21 ... Intermediate film.

Claims (9)

1. A resin film used for an interlayer of laminated glass, wherein the maximum value of tan δ at 25 ° C. and in the frequency range of 100 to 100,000 Hz is 0.5 to 4.0.
2. It is formed from a resin composition containing a polymer of a monomer containing a (meth) acryloyl compound,
   The resin film according to claim 1, wherein the weight average molecular weight of the polymer is 200,000 to 2,000,000.
3. The resin film according to claim 2, wherein the (meth) acryloyl compound contains an alkyl (meth) acrylate and a (meth) acrylate having a hydroxyl group.
4. The resin film according to claim 3, wherein the content of the alkyl (meth) acrylate is 50 to 95 parts by mass with respect to 100 parts by mass of the total amount of the monomers.
5. The resin film according to any one of claims 2 to 4, wherein the resin composition further comprises a thermal crosslinking agent.
6. The resin film according to any one of claims 1 to 5, wherein the haze is 10% or less.
7. An intermediate film of laminated glass, comprising: a base material; and a resin layer provided on the base material, wherein the resin layer is a layer comprising the resin film according to any one of claims 1 to 6. Film material.
8. A resin film according to any one of claims 1 to 6, comprising: two opposing glass plates; and an intermediate film sandwiched between the two glass plates. Glass.
9. A method for producing laminated glass, comprising: two opposing glass plates; and an intermediate film sandwiched between the two glass plates,
   A process of laminating the two glass plates via the resin film according to any one of claims 1 to 6 to obtain a laminate,
   Heating and pressing the laminate under conditions of 30 to 150 ° C. and 0.3 to 1.5 MPa;
   A method of producing laminated glass, including:

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