JP7333382B2 - Core-shell type polymer for interlayer film, resin composition, interlayer film for laminated glass - Google Patents

Description

TECHNICAL FIELD The present invention relates to a core-shell type polymer for interlayer film, a resin composition, and an interlayer film for laminated glass.

Laminated glass is used in various applications such as mobile bodies such as automobiles, buildings, and solar cells. Polyvinyl butyral resins, ionomer resins, and the like are known as materials for interlayer films for laminated glass.
In particular, ionomer resin films are excellent in transparency and adhesion to glass, and in comparison with polyvinyl butyral resin films, they are superior in hardness in the operating temperature range and have self-supporting properties. It can be suitably used as an intermediate film for laminated glass.

Attempts have also been made to use a core-shell polymer as an interlayer resin for laminated glass. Patent Document 1 discloses an interlayer film for laminated glass having at least a sound insulation layer made of a resin composition containing a thermoplastic resin and a damping agent. Acrylic core-shell resins are mentioned as thermoplastic resins.

WO2018/061861

The core-shell resin disclosed in Patent Document 1 aims at improving the sound insulation and transparency of the interlayer, and does not provide an interlayer having adhesiveness to glass and self-supporting properties. Therefore, an interlayer film having excellent adhesiveness to glass, in particular, sufficiently satisfying all of the adhesiveness to glass, transparency, and self-supporting properties required as an interlayer resin for laminated glass for structural materials is produced. No core-shell resin has been proposed so far.

The present invention has been made in view of the above-mentioned current situation, and provides a core-shell type interlayer film for laminated glass that is excellent in adhesiveness to glass, preferably adhesiveness to glass, transparency, and self-standing. An object of the present invention is to provide a polymer, a resin composition, and an interlayer film for laminated glass which is excellent in adhesiveness to glass, preferably adhesiveness to glass, transparency, and self-supporting property.

The present inventors have found that the core-shell type polymer described below, the resin composition containing the core-shell type polymer, and the interlayer film for laminated glass obtained by using the core-shell type polymer or the resin composition We have found that the above objects are achieved.

That is, the present invention relates to the following (1) to (10).
(1) A core-shell polymer having a core particle and a shell covering at least a portion of the core particle, wherein the content X _S (% by mass) of acetone-soluble matter with respect to the total mass of the core-shell polymer and acetone A core-shell polymer for an interlayer film of laminated glass, wherein the acid value A _s (mmol/g) of the soluble portion satisfies the following relationship.
X _S A _S ≧75
(2) The core-shell polymer for an interlayer film of laminated glass according to (1), wherein the core particles, the shell, or both of the core-shell polymer contains a (meth)acrylate polymer.
(3) The core particle is a coated core particle having an inner layer and a polymer coating covering at least a part of the surface of the inner layer, and the polymer coating contains the (meth)acrylate polymer of (2). Core-shell type polymer for interlayer film of laminated glass.
(4) A resin composition comprising the core-shell type polymer for an interlayer film of laminated glass according to any one of (1) to (3).
(5) The content X _S ' (% by mass) of the acetone-soluble matter and the acid value A _S ' (mmol/g) of the acetone-soluble matter with respect to the total mass of the resin composition satisfy the following relationship, ( 4) The resin composition.
X _S 'A _S '≧75
(6) The resin composition of (4) or (5), wherein the core particles, the shell, or both of the core-shell polymer contains a (meth)acrylate polymer.
(7) The core particle is a coated core particle having an inner layer and a polymer coating covering at least part of the surface of the inner layer, and the polymer coating contains the (meth)acrylate polymer. (6) any resin composition.
(8) In the morphology of the melt-kneaded product of the resin composition observed with an electron microscope, the shell forms a continuous phase, the core particles form a dispersed phase, and the dispersed phase has an average particle size of 200 nm or less. The resin composition according to any one of (4) to (7).
(9) An interlayer film for laminated glass, comprising at least one film obtained by molding the resin composition according to any one of (4) to (8).
(10) A laminated glass comprising the interlayer for laminated glass of (9) disposed between two glass plates.

According to the present invention, a core-shell type polymer, a resin composition, and a glass that provide an interlayer film for laminated glass having excellent adhesiveness to glass, preferably excellent adhesiveness to glass, transparency, and self-supporting properties. It is possible to obtain an interlayer film for laminated glass which is excellent in adhesiveness, preferably adhesiveness to glass, transparency, and self-supporting property.

Core-Shell Polymer The core-shell polymer of the present invention has a core particle and a shell covering at least a portion of the core particle surface, preferably at least 50% (including 100%) of the total surface.

Core Particles The core particles (including coated core particles described later; hereinafter the same) in the present invention contain the polymer (A). The polymer (A) is obtained by polymerizing the monomer (a) and arbitrary monomers such as a polyfunctional grafting agent and a polyfunctional cross-linking agent.
The monomer (a) is not particularly limited as long as it does not impair the effects of the present invention. Examples include (meth)acrylic acid and salts thereof; methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid alkyl esters such as n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; hydroxyalkyl (meth)acrylates, (Meth)acrylic acid-substituted alkyl esters such as (meth)acrylic acid N,N'-dialkylaminoalkyl esters; N-alkyls such as (meth)acrylamide, N-methyl(meth)acrylamide, and N-ethyl(meth)acrylamide -(meth)acrylamide; styrene, α-methylstyrene, 1-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-( aromatic vinyl compounds such as phenylbutyl)styrene and halogenated styrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; butadiene, isoprene, 2,3-dimethylbutadiene, 2-methyl-3-ethylbutadiene, 1 ,3-pentadiene, 3-methyl-1,3-pentadiene, 2-ethyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene, 3,4-dimethyl-1,3 -conjugated diene compounds such as hexadiene, 1,3-heptadiene, 3-methyl-1,3-heptadiene, 1,3-octadiene, cyclopentadiene, chloroprene, and myrcene;
From the viewpoint of productivity of the core-shell polymer, the monomer (a) is preferably selected from (meth)acrylic acid alkyl esters, aromatic vinyl compounds, and conjugated diene compounds. It is more preferably selected from acid alkyl esters and aromatic vinyl compounds, and more preferably selected from (meth)acrylic acid alkyl esters.
Monomer (a) may be used alone or in combination of two or more.

Polyfunctional Grafting Agent In forming the polymer (A), a polyfunctional grafting agent may be used as an optional component. That is, the polymer (A) may contain structural units derived from the polyfunctional grafting agent in addition to the structural units derived from the monomer (a).
A multifunctional grafting agent is used to chemically bond the core particle and the shell. In some cases, it is also used for cross-linking the polymers (A). When the core particle is a coated core particle described later, the polyfunctional grafting agent is used to chemically bond the inner layer and the polymer coating and/or chemically bond the polymer coating and the shell. be done.
As the polyfunctional grafting agent, any polyfunctional monomer having the above functions can be used, and compounds having two or more different polymerizable groups are generally preferably used. Specific examples of polyfunctional grafting agents include allyl (meth)acrylate, methallyl (meth)acrylate, allyl cinnamate, methallyl cinnamate, monoallyl maleate, diallyl maleate, monoallyl fumarate, diallyl fumarate, phthalate Examples include diallyl acid, diallyl terephthalate, and diallyl isophthalate. Among these, allyl methacrylate is preferred because it provides good chemical bonding between the core particles and the shell.

From the viewpoint of maintaining the structure of the core-shell type polymer during molding, the amount of the polyfunctional grafting agent used in the formation of the polymer (A) is adjusted to an appropriate range of the content of the acetone-soluble component described later. From the viewpoint, it is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, based on the total mass of the monomers (a) used to form the polymer (A). When the content of the polyfunctional grafting agent is 0.01% by mass or more, the bonding between the core particles and the shell is sufficient, and the breakage of the core-shell polymer during molding can be prevented. When it is 5% by mass or less, the impact resistance of the core-shell polymer is good.

Polyfunctional Crosslinking Agent In forming the polymer (A), a polyfunctional crosslinking agent can be used, if desired. The polyfunctional cross-linking agent cross-links the polymer (A) in the core particles, the polymer (A) in the inner layer in the case of the coated core particles, or the polymer (A) in the polymer coating. It is used to prevent the core-shell structure from breaking during molding. That is, the polymer (A) may contain one or both of a structural unit derived from a polyfunctional grafting agent and a structural unit derived from a polyfunctional cross-linking agent in addition to the structural unit derived from the monomer (a). good.
As the polyfunctional crosslinking agent, in addition to the polyfunctional grafting agents described above, any polyfunctional monomer capable of crosslinking the polymer (A) during polymerization can be used. For example, conventionally known polyfunctional cross-linking agents such as di(meth)acrylic compounds, diallyl compounds, divinyl compounds, and trivinyl compounds can be used. More specifically, for example, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, divinyl Benzene, trivinylbenzene, ethylene glycol diallyl ether, propylene glycol diallyl ether, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and the like can be mentioned, and one or more of these can be used. can be done.

As described above, the polymer (A) is also crosslinked to some extent by the polyfunctional grafting agent, so the use of the polyfunctional crosslinking agent is not absolutely necessary. When using a polyfunctional cross-linking agent, it is preferably 0.5% by mass or less with respect to the total mass of the monomer (a). When it is 0.5% by mass or less, the polymer (A) is not excessively crosslinked, and good impact resistance can be maintained.

Since the polymer (A) highly crosslinked with a polyfunctional crosslinking agent does not dissolve in a solvent, its weight average molecular weight cannot be measured. The weight average molecular weight of the uncrosslinked polymer (A) is not particularly limited as long as it does not impair the effects of the present invention, preferably 5,000 to 1,000,000, more preferably 10,000 to 900,000, More preferably 30,000 to 800,000, particularly preferably 70,000 to 700,000. The weight average molecular weight can be determined by gel permeation chromatography using standard polystyrene calibrations.

Other Polymer The core particles may be formed of the polymer (A) alone, or may be formed of a mixture containing the polymer (A) and another polymer. Examples of other polymers include polyvinyl alcohol resins, polyvinyl acetal resins, polyurethane resins, polyvinyl carboxylate resins, olefin-vinyl carboxylate copolymers, polyester elastomer resins, and halogenated polyolefin resins.

Structure of Core Particle The core particle may be a single-layer particle, or a particle consisting of a plurality of layers, for example, a core particle having an inner layer and a polymer coating covering at least a part of the surface of the inner layer. may be In the present specification, the core particles having the inner layer and the polymer coating are sometimes referred to as "coated core particles". In the present specification, the term "coating" means that the surface of the polymer particles forming the inner layer is coated with a polymer coating at least partially, preferably at least 50% (including 100%) of the entire surface. This refers to a state in which the entire surface may be covered.

The inner layer and the polymer coating may be formed of the polymer (A) alone, or may be formed of a mixture containing the polymer (A) and the other polymer described above. The polymer (A) forming the inner layer and the polymer (A) forming the polymer coating may be the same or different, but are preferably different.

In the formation of the inner layer and the polymer coating, it is preferable to use the polyfunctional grafting agent from the viewpoint of maintaining the structure of the core-shell type polymer during molding. Examples and preferred examples of polyfunctional grafting agents are the same as described above.
Further, in the formation of the inner layer and the polymer film, the amount of the polyfunctional grafting agent used, if necessary, is the total mass of the monomer (a) from the viewpoint of maintaining the structure of the core-shell type polymer during molding. It is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, based on the total amount of the monomer (a) used for forming the inner layer and the polymer film.

The mass ratio of the inner layer and the polymer coating is preferably 1: (0.01 to 100), more preferably 1: (0.02 to 90), further preferably 1: (0.04 to 80), 1: ( 0.05 to 50) are particularly preferred.

Shell The shell of the core-shell polymer of the present invention contains the polymer (B).
The monomer (b) forming the polymer (B) of the present invention is not particularly limited as long as it does not impair the effects of the present invention, and is selected from the monomers described for the monomer (a). Accordingly, the polymer (B) may be the same as or different from the polymer (A) forming the core particles (including the coated core particles), but preferably they are different. Preferably selected from (meth) acrylic acid, (meth) acrylic acid salts, (meth) acrylic acid alkyl esters, aromatic vinyl compounds, and conjugated diene compounds, more preferably (meth) acrylic acid, (meth) ) acrylic acid salts, (meth)acrylic acid alkyl esters, and aromatic vinyl compounds, more preferably (meth)acrylic acid, (meth)acrylic acid salts, and (meth)acrylic acid alkyl esters selected, particularly preferably selected from (meth)acrylic acid and (meth)acrylic acid alkyl esters. Monomer (b) may be used alone or in combination of two or more.

The shell of the core-shell polymer of the present invention preferably contains a monomer having an acidic functional group as the monomer (b) forming the polymer (B). From the viewpoint of adjusting the acid value of the acetone-soluble portion to be described later in an appropriate range, it is preferable that the monomer having an acidic functional group is contained in an amount of 7% by mass or more based on the total mass of the core-shell polymer, and 10% by mass. % or more, more preferably 15 mass % or more. Although the upper limit is not particularly limited, it may be, for example, 50% by mass or less. In addition, as a monomer which has an acidic functional group, (meth)acrylic acid etc. are mentioned, for example.

Chain Transfer Agent It is preferred to use a chain transfer agent in forming the polymer (B). By adding a chain transfer agent to adjust the molecular weight of the polymer (B), the finally obtained core-shell type polymer has improved fluidity during molding and excellent moldability. The type of chain transfer agent is not particularly limited, and conventionally known ones can be used. xanthogen disulfides such as dimethylxanthogen disulfide and diethylxanthogen disulfide; thiuram disulfides such as tetrathiuram disulfide; and halogenated hydrocarbons such as carbon tetrachloride and ethylene bromide.

The amount of the chain transfer agent used is determined from the viewpoint of compatibility between the fluidity during molding of the core-shell type polymer and the impact resistance, and from the viewpoint of adjusting the content of the acetone-soluble matter described below to an appropriate range. 0.01 to 5% by weight is preferred, and 0.025 to 3% by weight is more preferred, based on the total weight of monomer (b).

Since the polymer (B) highly crosslinked with a polyfunctional crosslinker does not dissolve in a solvent, its weight average molecular weight cannot be measured. The weight average molecular weight of the uncrosslinked polymer (B) is not particularly limited as long as it does not impair the effects of the present invention, preferably 5,000 to 1,000,000, more preferably 10,000 to 900,000, More preferably 30,000 to 800,000, particularly preferably 70,000 to 700,000. The weight average molecular weight can be determined by gel permeation chromatography using standard polystyrene calibrations.

Other Polymers The shell may be formed from the above polymer (B) alone, or may be formed from a mixture containing the polymer (B) and another polymer. Said other polymers are the same as the other polymers described for the core particles.

In the core-shell polymer of the present invention, the mass ratio of the core particles (including the coated core particles) and the shell is preferably 1: (0.1 to 100), more preferably 1: (0.02 to 90). : (0.04 to 80) is more preferred, and 1: (0.05 to 50) is particularly preferred.

The average particle size of the core-shell polymer of the invention is preferably 10 to 500 nm, more preferably 25 to 300 nm, even more preferably 50 to 200 nm, particularly preferably 60 to 160 nm.
In the present invention, the average particle diameter is the median diameter when the particle size distribution of the core-shell polymer emulsion is measured on a volume basis using a dynamic light scattering measurement device.

The average particle size of the core particles (including coated core particles) in the core-shell polymer of the present invention is preferably 5 to 300 nm, more preferably 10 to 250 nm, even more preferably 15 to 200 nm, particularly preferably 20. ~150 nm.
The average particle size of the core particles was calculated from the average value of the particle sizes of the core particles in 10 or more core-shell polymers observed with a transmission electron microscope.

Manufacturing method of core-shell type polymer (for single-layer core particles)
The production method of the core-shell type polymer is not particularly limited, but it can be produced, for example, by emulsion polymerization or suspension polymerization.
From the standpoint of ease of production, the core-shell type polymer is preferably produced by emulsion polymerization including steps 1 and 2 below.
Step 1: A step of emulsion-polymerizing one or more monomers (a) in water to obtain an emulsified liquid 1 containing core particles.
Step 2: Further, one or more monomers (b) are added to the emulsion 1 obtained in Step 1 and emulsion-polymerized in water to form a shell, which contains a core-shell type polymer. a step of obtaining an emulsified liquid 2;

Manufacturing method of core-shell type polymer (for coated core particles)
When the core particles of the core-shell type polymer are coated core particles, they are preferably obtained by a manufacturing method including the following steps 1', 2' and 3'.
Step 1′: A step of emulsion-polymerizing one or more monomers (a) in water to obtain emulsion 1′ containing monolayer core particles (inner layer of coated core particles).
Step 2′: One or more monomers (a) are further added to the emulsion 1′ obtained in Step 1′ and emulsion polymerization is carried out in water to form a polymer film, which is then coated. A step of obtaining an emulsion 2' containing core particles.
Step 3′: One or more monomers (b) are further added to the emulsion 2′ obtained in Step 2′ and emulsion polymerization is carried out in water to form a shell to form a core-shell polymerization. A step of obtaining an emulsion 3' containing coalescence.
When the core particle consists of three or more layers, it can be produced by repeating the above step 2′.

An emulsifier is usually used in the emulsion polymerization. Examples of the emulsifier include anionic surfactants such as sodium alkylbenzenesulfonate, sodium lauryl sulfate, sodium higher fatty acid and rosin soap; nonionic surfactants such as polyoxyethylene alkyl ether and nonylphenol ethoxylate; Cationic surfactants such as stearyldimethylammonium and benzalkonium chloride; amphoteric surfactants such as cocamidopropyl betaine and cocamidopropyl hydroxysultaine. Polymers such as partially saponified polyvinyl alcohol (degree of saponification 70 to 90 mol%), polyvinyl alcohol modified with mercapto group (degree of saponification 70 to 90 mol%), β-naphthalenesulfonic acid formalin condensate salt, ethyl (meth)acrylate copolymer, etc. It is also possible to use surfactants. These emulsifiers may be used alone or in combination of two or more. The amount of the emulsifier used is preferably 0.01 to 40% by mass, more preferably 0.05 to 20% by mass, relative to water used as a dispersion medium.

A radical polymerization initiator is usually used in the emulsion polymerization. Examples of the radical polymerization initiator include water-soluble inorganic polymerization initiators, water-soluble azo polymerization initiators, oil-soluble azo polymerization initiators, organic peroxides, and the like. A redox polymerization initiator may also be used as the radical polymerization initiator.

Water-soluble inorganic polymerization initiators include hydrogen peroxide, sodium peroxodisulfate, potassium peroxodisulfate and the like.
Water-soluble azo polymerization initiators include 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2′-azobis[2-(2-imidazolin-2-yl ) propane]disulfate dihydrate, 2,2′-azobis(2-methylpropionamidine) dihydrochloride, 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2'-azobis [2-methyl-N-(2-hydroxyethyl)propionamide] and the like.

Oil-soluble azo polymerization initiators include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2' -azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methyl ethyl)azo]formamide, 2,2′-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2′-azobis(N-butyl-2-methylpropionamide), dimethyl-2, 2-azobis(isobutyrate) and the like.

Examples of organic peroxides include diacyl peroxides such as bis-3,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide and dibenzyl peroxide; 1,1,3,3-tetramethylbutyl hydroperoxide; , cumene hydroperoxide, hydroperoxides such as t-butyl hydroperoxide; dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t -butylperoxyisopropyl)benzene, t-butylcumyl peroxide, di-t-butyl peroxide, dialkyl peroxides such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3; 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 1,1-di-t-butylperoxycyclohexane, 2,2-di-t-butylperoxybutane and other peroxy Ketal; 1,1,3,3-tetramethyl butyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2- ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, Alkyl peroxyesters such as t-butyl peroxyacetate and t-butyl peroxybenzoate; di-2-ethylhexylperoxydicarbonate, diisopropylperoxydicarbonate, t-butylperoxyisopropylcarbonate, t-butylperoxy- peroxycarbonates such as 2-ethylhexyl carbonate and 1,6-bis(t-butylperoxycarbonyloxy)hexane;

The amount of the radical polymerization initiator used is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.5% by mass, relative to water used as a dispersion medium.

Moreover, from the viewpoint of productivity, a redox polymerization initiator may be used, and as the redox polymerization initiator, the organic peroxide and the transition metal salt are preferably used in combination.
Examples of transition metal salts used in combination with organic peroxides include iron sulfate (II), iron thiosulfate (II), iron carbonate (II), iron chloride (II), iron bromide (II), and iron iodide. (II), iron compounds such as iron hydroxide (II), iron oxide (II); copper sulfate (I), copper thiosulfate (I), copper carbonate (I), copper chloride (I), copper bromide ( I), copper (I) iodide, copper (I) hydroxide, copper compounds such as copper (I) oxide, or hydrates thereof. Among these, from the viewpoint of productivity, cumene hydroperoxide and an iron compound may be used in combination, and cumene hydroperoxide and iron (II) sulfate hydrate may be used in combination.

A reducing agent may also be used together with the radical polymerization initiator. Examples of the reducing agent include iron compounds such as iron (II) chloride and iron (II) sulfate; sodium salts such as sodium hydrogensulfate, sodium bisulfite, sodium sulfite, sodium hydrogensulfite and sodium hydrogencarbonate; ascorbic acid, Rongalit, Organic reducing agents such as sodium diotinate, triethanolamine, glucose, fructose, glyceraldehyde, lactose, arabinose, and maltose are included. The iron compound and the organic reducing agent may be used together.
The amount of the reducing agent used is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.5% by mass, relative to water used as a dispersion medium.

In the production method, if necessary, a metal ion chelating agent may be added to the emulsion polymerization system. Specific examples include metal ion chelating agents such as disodium dihydrogen ethylenediaminetetraacetate.
In the above production method, an electrolyte may be added as a thickening inhibitor to the emulsion polymerization system, if necessary. Specific examples include electrolytes such as sodium chloride, sodium sulfate, and trisodium phosphate. In the production method, when an emulsifier and a thickening inhibitor are used in combination, the amount of the thickening inhibitor used is preferably 20% by mass or less relative to the emulsifier, from the viewpoint of the stability of the micelles in the emulsion. % by mass or less is more preferable, and 5% by mass or less is even more preferable.
The reducing agent, metal ion chelating agent and electrolyte may be added during the polymerization reaction, but are preferably added to water from the beginning of the emulsion polymerization.

In the production method, if necessary, a chain transfer agent may be added to the emulsion polymerization system. Chain transfer agents include mercaptans such as n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, hexadecylmercaptan and n-octadecylmercaptan; - Thiols such as mercaptopropionic acid, β-methyl β-mercaptopropionate, 2-ethylhexyl β-mercaptopropionate, 3-methoxybutyl β-mercaptopropionate, 2-mercaptoethanol, 3-mercapto-1,2-propanediol ; A hydrocarbon compound having a large chain transfer constant such as α-methylstyrene dimer can be used.

When using a water-soluble radical polymerization initiator, it may be added as an aqueous solution, but when using a water-insoluble radical polymerization initiator, an emulsified liquid of the radical polymerization initiator is prepared in advance using water and an emulsifier. , which may be added. In this case, the emulsifier used may be the same as or different from that used in the emulsion polymerization. Moreover, you may combine 2 or more types of emulsifiers.

From the viewpoint of the viscosity and stability of the emulsion, the amount of water (dispersion medium) used in the emulsion polymerization is the total amount of the monomers used in the production of the core-shell polymer, that is, the core particles (coating particles) of the core-shell polymer. The monomers (monomer (a), and optional multifunctional grafting agent and multifunctional cross-linking agent) used to prepare the core particles) and the monomers used to prepare the shell (monomers ( b), and any polyfunctional grafting agent and polyfunctional cross-linking agent), with respect to 100 parts by weight, preferably 50 to 1,500 parts by weight, more preferably 80 to 1,000 parts by weight, and 100 ~800 parts by mass is more preferable.
The polymerization temperature of the emulsion polymerization is preferably 0 to 100°C, and preferably 50 to 90°C from the viewpoint of increasing the polymerization rate.

In the present invention, the emulsion after emulsion polymerization may be used as it is, or the core-shell type polymer may be recovered and used by known methods such as salting out, acid precipitation, freezing, and solvent addition. The recovered core-shell polymer may be further purified by known methods such as washing, reprecipitation, steam stripping and the like.

In the present invention, from the viewpoint of suppressing deterioration of the core-shell type polymer, anti-aging agents, antioxidants, and heat-degradation inhibitors are added to the emulsion after emulsion polymerization, or to the core-shell type polymer after recovery treatment or purification treatment. At least one selected may be added. From the viewpoint of suppressing the deterioration of the core-shell type polymer during the recovery process and purification process after the polymerization reaction, these inhibitors are added to the emulsion after emulsion polymerization, and then the core-shell type polymer is removed. Recovery treatment or purification treatment may be performed.

A known material can be used as the anti-aging agent. Specifically, hydroquinone, hydroquinone monomethyl ether, 2,5-di-t-butylphenol, 2,6-di(t-butyl)-4-methylphenol, mono (or di, or tri) (α-methylbenzyl ) Phenolic compounds such as phenol; 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis bisphenol compounds such as (3-methyl-6-t-butylphenol); benzimidazole compounds such as 2-mercaptobenzimidazole and 2-mercaptomethylbenzimidazole; 6-ethoxy-1,2-dihydro-2,2, Amine-ketone compounds such as 4-trimethylquinoline, reaction product of diphenylamine and acetone, 2,2,4-trimethyl-1,2-dihydroquinoline polymer; N-phenyl-1-naphthylamine, alkylated diphenylamine, octylation Aromatic secondary amine compounds such as diphenylamine, 4,4′-bis(α,α-dimethylbenzyl)diphenylamine, p-(p-toluenesulfonylamido)diphenylamine, N,N′-diphenyl-p-phenylenediamine; Thiourea compounds such as 1,3-bis(dimethylaminopropyl)-2-thiourea and tributylthiourea can be used.

Antioxidants are effective by themselves to prevent oxidation deterioration of resins in the presence of oxygen. Examples include phosphorus antioxidants, hindered phenol antioxidants, thioether antioxidants, and the like. These antioxidants may be used alone or in combination of two or more. Among them, from the viewpoint of the effect of preventing deterioration of optical properties due to coloring, phosphorus antioxidants and hindered phenol antioxidants are preferable, and combined use of phosphorus antioxidants and hindered phenol antioxidants is more preferable.
When a phosphorus-based antioxidant and a hindered phenol-based antioxidant are used in combination, the amount of phosphorus-based antioxidant used: the amount of hindered phenol-based antioxidant used is in a mass ratio of (1:5) to (2:1) is preferred, and (1:2) to (1:1) are more preferred.

Phosphorus-based antioxidants include 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite (manufactured by ADEKA Corporation; trade name: ADEKA STAB HP-10), tris (2,4- Di-t-butylphenyl)phosphite (manufactured by BASF; trade name: IRGAFOS168), 3,9-bis(2,6-di-t-butyl-4-methylphenoxy)-2,4,8,10- Tetraoxa-3,9-diphosphaspiro[5.5]undecane (manufactured by ADEKA Corporation; trade name: ADEKA STAB PEP-36) and the like are preferred.

Hindered phenol-based antioxidants include pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF; trade name IRGANOX1010), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate (manufactured by BASF; trade name IRGANOX1076) and the like are preferred.

Thermal degradation inhibitors can prevent thermal degradation of resins by scavenging polymer radicals generated when exposed to high heat under substantially oxygen-free conditions.
Examples of the heat deterioration inhibitor include 2-t-butyl-6-(3′-t-butyl-5′-methyl-hydroxybenzyl)-4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd.; trade name Sumilizer GM). ), 2,4-di-t-amyl-6-(3′,5′-di-t-amyl-2′-hydroxy-α-methylbenzyl)phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd.; trade name Sumilizer GS) and the like are preferred.

In the present invention, in addition to the anti-aging agent, antioxidant, and heat deterioration inhibitor described above, the core-shell type polymer may optionally include an ultraviolet absorber, a light stabilizer, an anti-adhesion agent, a lubricant, a release agent, Various additives such as polymer processing aids, antistatic agents, flame retardants, dyes and pigments, organic dyes, matting agents, and phosphors may be added. The amount of such various additives can be appropriately determined within a range that does not impair the effects of the present invention, and the total amount is preferably 7% by mass or less, more preferably 5% by mass. 4% by mass or less, and more preferably 4% by mass or less.
Various additives may be added to the polymerization reaction solution when producing the core-shell type polymer, may be added to the core-shell type polymer produced by the polymerization reaction, or may be added during production of the molded product. You may

An ultraviolet absorber is a compound having the ability to absorb ultraviolet rays, and is said to have a function of mainly converting light energy into heat energy.
Examples of ultraviolet absorbers include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic acid esters, formamidines and the like. These may be used individually by 1 type, or may use 2 or more types together.

Benzotriazoles are preferable as UV absorbers because they are highly effective in suppressing deterioration of optical properties such as coloration due to exposure to UV rays. Examples of benzotriazoles include 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (manufactured by BASF; trade name TINUVIN329), 2-(2H- benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (manufactured by BASF; trade name TINUVIN234), 2,2′-methylenebis[6-(2H-benzotriazole-2 -yl)-4-t-octylphenol] (manufactured by ADEKA; LA-31), 2-(5-octylthio-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol, etc. is preferred.

Further, as a triazine ultraviolet absorber, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine (manufactured by ADEKA Corporation; LA- F70) and its analogues, hydroxyphenyltriazine-based UV absorbers (manufactured by BASF; TINUVIN477 and TINUVIN460), 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3, 5-triazine and the like can be mentioned.

A photostabilizer is a compound that is said to have a function of scavenging radicals generated mainly by oxidation by light. Suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.

As the anti-tacking agent, fatty acid salts or esters, polyhydric alcohol esters, inorganic salts, inorganic oxides, and particulate resins are preferred. Specific examples include calcium stearate, calcium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, silicon dioxide (manufactured by Evonik; trade name Aerosil), and particulate acrylic resins.

Lubricants include, for example, stearic acid, behenic acid, stearamic acid, methylenebisstearamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, hydrogenated oil and the like.

Release agents include higher alcohols such as cetyl alcohol and stearyl alcohol; glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride;

As the polymer processing aid, polymer particles having a particle size of 0.05 to 0.5 μm, which can be produced by an emulsion polymerization method, are usually used. The polymer particles may be monolayer particles composed of a polymer having a single composition ratio and a single intrinsic viscosity, or may be multilayer particles composed of two or more polymers having different composition ratios or intrinsic viscosities. may Among these, particles having a two-layer structure having an inner layer of a polymer layer having a low intrinsic viscosity and an outer layer of a polymer layer having a high intrinsic viscosity of 5 dl/g or more are preferred. The polymeric processing aid preferably has a limiting viscosity of 3 to 6 dl/g. If the intrinsic viscosity is too low, the moldability-improving effect tends to be low. If the intrinsic viscosity is too high, there is a tendency for the copolymer to deteriorate in moldability.

A compound having a function of converting ultraviolet light into visible light is preferably used as the organic dye.

Examples of phosphors include fluorescent pigments, fluorescent dyes, fluorescent white dyes, fluorescent whitening agents, and fluorescent bleaching agents.

The core-shell polymer of the present invention is useful for producing interlayer films for laminated glass. Accordingly, the present invention also relates to a core-shell type polymer for an interlayer film of laminated glass.

Resin composition The resin composition of the present invention contains the core-shell polymer in an amount of preferably 50% by mass or more (including 100%), more preferably 70% by mass or more (including 100%), and still more preferably 90% by mass. Above (including 100%).

The resin composition of the present invention may optionally contain other thermoplastic resins in addition to the core-shell type polymer. Examples of the other thermoplastic resins include, but are not limited to, (meth)acrylic resins, polyvinyl butyral resins, and ionomer resins.

When the resin composition contains the other thermoplastic resin, the content thereof is preferably 50% by mass or less, more preferably 30% by mass or less, relative to the total mass of the resin composition. It is more preferably 10% by mass or less. When the content of the other thermoplastic resin in the resin composition is 50% by mass or less, the adhesion to substrates such as glass is good.

The resin composition of the present invention contains, in addition to the core-shell type polymer and optionally other thermoplastic resins, an antioxidant, an ultraviolet absorber, a light stabilizer, an adhesive, as long as the effects of the present invention are not impaired. Various additives such as force modifiers, antiblocking agents, pigments, dyes, etc. may be included.

The method for producing the resin composition of the present invention is not particularly limited, and it can be obtained by mixing the core-shell type polymer with the other thermoplastic resin, additives and other optional components according to a known production method.

The resin composition of the present invention is useful for producing interlayer films for laminated glass. Accordingly, the present invention also relates to a resin composition for an interlayer film for laminated glass.

Glass transition temperature of core particles The glass transition temperature (Tg) of core particles not containing coated core particles is preferably -100 to 40°C, more preferably -70 to 20°C, and even more preferably -60 to 0°C. . When the glass transition temperature is within the above range, the core particles exhibit rubber elasticity, and the resulting intermediate film has good impact resistance and penetration resistance.
The glass transition temperature of the core particles can be adjusted, for example, by selecting the monomers forming the core particles.
The glass transition temperature can be measured with a differential scanning calorimeter by the method described in JIS K6240 (2011).
In the case of coated core particles, the glass transition temperature of at least one of the inner layer and the polymer coating is preferably -100 to 40°C, more preferably -70 to 20°C, and even more preferably -60 to 0°C.

Acetone-soluble content The content of the acetone-soluble content of the core-shell polymer of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 10% by mass, based on the total mass of the core-shell polymer. ~90% by mass, more preferably 12.5 to 87.5% by mass, even more preferably 15 to 85% by mass, even more preferably 17.5 to 82.5% by mass, particularly preferably 20 to 80% by mass is.
The content of acetone-soluble matter in the resin composition of the present invention is not particularly limited, but is preferably 10% by mass or more, preferably 10 to 90% by mass, based on the total mass of the resin composition. More preferably 12.5 to 87.5% by mass, still more preferably 15 to 85% by mass, even more preferably 17.5 to 82.5% by mass, and particularly preferably 20 to 80% by mass. When the content of the acetone-soluble matter is within the above range, the obtained interlayer film has good adhesion to substrates such as glass.
The content of acetone solubles is
The core-shell type polymer or resin composition is immersed in acetone,
Centrifuge the acetone-insoluble matter and acetone-soluble matter in a centrifuge,
Remove acetone soluble matter,
Measure the mass of the obtained acetone-insoluble matter,
It is a value calculated from the following formula (1).
Details are provided in the examples below.

Acetone soluble content = (Mc-Ma) / Mc x 100 (1)
In the formula, Mc is the mass (g) of the core-shell polymer or resin composition, and Ma is the mass (g) of the acetone-insoluble matter.

The content of the acetone-soluble component can be adjusted, for example, by changing the amount of the shell in the core-shell polymer and/or changing the degree of chemical bonding between the core particles (including the coated core particles) and the shell. can be adjusted by When the monomers constituting the shell contained in the core-shell polymer do not contain the polyfunctional grafting agent and the polyfunctional cross-linking agent, and/or when a chain transfer agent is used in the polymerization of the shell, , easily soluble in acetone.

Acid value of acetone-soluble matter The acid value of the acetone-soluble matter is not particularly limited, but is preferably 0.5 to 10.0 mmol/g, more preferably 0.55 to 9.50 mmol/g. more preferably 0.6 to 9.0 mmol/g, even more preferably 0.65 to 8.5 mmol/g, more preferably 0.7 to 8.25 mmol/g More preferably, it is particularly preferably 0.75 to 8.0 mmol/g. When the acid value of the acetone-soluble component is within the above range, the adhesion of the obtained interlayer film to a substrate such as glass can be further improved.
The acid value of acetone solubles is
The core-shell type polymer or resin composition is immersed in acetone,
Centrifuge the acetone-insoluble matter and acetone-soluble matter in a centrifuge,
Remove acetone insoluble matter,
It can be determined by neutralization titration of the resulting solution of acetone-soluble matter with a basic solution.
Details are provided in the examples below.

The method for adjusting the acid value of the acetone-soluble component is not particularly limited. For example, a monomer unit having an acidic functional group (e.g., (meth) acrylic acid unit) can be adjusted by the amount to be introduced.

In the core-shell polymer of the present invention, the product X _S A S of the content X _S (% by mass) _of the acetone-soluble matter and the acid value A _S (mmol/g) of the acetone-soluble matter is 75 or more. is preferably 80 or more, more preferably 85 or more, even more preferably 90 or more, even more preferably 95 or more, even more preferably 100 or more, and 110 It is more preferably 120 or more, and particularly preferably 140 or more.
The upper limit of the product X _S A _S is preferably 900, more preferably 800, even more preferably 700, still more preferably 600, still more preferably 500, still more preferably 400, still more preferably 300, more preferably More preferably 250, particularly preferably 200.
The above lower limit value and the above upper limit value of the product X _S A _S can be arbitrarily combined.
In one aspect of the present invention, the product X _S A _S is within the above range, and the content X _S of acetone-soluble matter and the acid value A _S of acetone-soluble matter are each within the above range. Preferably.
When the product of the content of the acetone-soluble matter and the acid value is within the above range, the obtained interlayer film has good adhesion to substrates such as glass.

Furthermore, in the resin composition containing the core-shell polymer of the present invention, the content X _S ' (% by mass) of the acetone-soluble matter and the acid value A _S ' (mmol/g) of the acetone-soluble matter The product X _S 'A _S ' is preferably 75 or more, more preferably 80 or more, even more preferably 85 or more, even more preferably 90 or more, and 95 or more. It is even more preferably 100 or more, even more preferably 110 or more, even more preferably 120 or more, and particularly preferably 140 or more.
The upper limit of the product X _S 'A _S ' is preferably 900, more preferably 800, still more preferably 700, still more preferably 600, still more preferably 500, still more preferably 400, still more preferably 300 , more preferably 250, particularly preferably 200.
The above lower limit value and above upper limit value of the product X _S 'A _S ' can be combined arbitrarily.
In one aspect of the present invention, the product X _S 'A _S ' is within the above range, and the content X _S ' of acetone-soluble matter and the acid value A _S ' of acetone-soluble matter are each the above is preferably within the range.
When the product of the content of the acetone-soluble matter and the acid value is within the above range, the obtained interlayer film has good adhesion to substrates such as glass. The reason for this is considered as follows.

The adhesion of the interlayer film to a substrate such as glass is improved by interaction between the functional group on the substrate side and the acidic functional group on the interlayer film side at the interface between the substrate and the interlayer film. Therefore, the present inventors paid attention to the amount of effective acidic functional groups that can contribute to the improvement of adhesion to substrates.
The effective amount of acidic functional groups is represented by the following formula:
Effective acidic functional group amount = X x Y
X: Area fraction of the acidic functional group-containing resin on the surface of the intermediate film in contact with the base material Good adhesion to substrates.
The area fraction of the acidic functional group-containing resin is proportional to the volume fraction of the acidic functional group-containing resin, and the volume fraction is proportional to the acetone-soluble content (X _S ).
The surface density of the acidic functional groups is proportional to the volume density of the acidic functional groups in the acidic functional group-containing resin, and the volume density is proportional to the acid value (A _S ) of the acetone-soluble component.
Therefore, the amount of effective acidic functional groups is proportional to the product of the content of acetone-soluble matter (X _S ) and the acid value of the acetone-soluble matter (A _S ). Based on the above ideas, as a result of extensive studies, it was found that the adhesion of the interlayer film to a substrate such as glass is determined by the content of acetone-soluble matter (X _S ) and the acid value of acetone-soluble matter (A _S ). We have found that it depends on the product X _S A _S , and based on this finding we have found a suitable range for the product X _S A _S as described above.

Glass transition temperature of acetone-soluble matter The glass transition temperature (Tg) of the acetone-soluble matter is preferably 40°C or higher, more preferably 40 to 200°C, and more preferably 50 to 180°C. More preferably, it is particularly preferably 60 to 160°C. When the glass transition temperature is within the above range, the self-supporting property of the intermediate film to be obtained is improved.
The glass transition temperature of the acetone solubles can be adjusted, for example, by selecting the monomers that form the shell.
The glass transition temperature can be measured by the method described above.

Weight-average molecular weight of acetone-soluble matter The weight-average molecular weight (Mw) of the acetone-soluble matter is preferably 5,000 to 1,000,000, more preferably 10,000 to 900,000. , 30,000 to 800,000, and particularly preferably 70,000 to 700,000. When the weight-average molecular weight is within the above range, moldability and mechanical properties of the obtained intermediate film are improved. The weight average molecular weight can be determined by gel permeation chromatography using standard polystyrene calibrations.

Morphology of the melt-kneaded product of the resin composition In the morphology of the melt-kneaded product of the resin composition of the present invention observed with an electron microscope, the shell of the core-shell polymer is a continuous phase, and the core particles (including coated core particles) are Forms a dispersed phase. The average particle size of the dispersed phase is preferably 200 nm or less, more preferably 10 to 200 nm, even more preferably 20 to 180 nm, particularly preferably 30 to 160 nm. When the average particle size of the dispersed phase is within the above range, the transparency of the resulting intermediate film is improved. The average particle size of the dispersed phase can be adjusted, for example, by changing the mass of the core particles and the amount of the emulsifier used during the production of the core-shell polymer.
In the present invention, the average particle size was obtained by the following method.
The resin composition was melt-kneaded at 200° C. and 100 rpm for 3 minutes to obtain a melt-kneaded resin composition.
The resulting melt-kneaded product was compression molded at 210° C. and a pressure of 50 kgf/cm ² for 5 minutes to obtain a resin sheet with a thickness of 0.8 mm.
The obtained resin sheet was observed with an electron microscope (SEM).
From the measured values of the short diameter and long diameter of the dispersed phase, the particle diameter was obtained by the following formula (2).
Particle diameter = (minor diameter + major diameter) / 2 (2)
The particle size of 100 dispersed phases was determined, and the average value was taken as the average particle size of the dispersed phase.

Storage modulus (E') of melt-kneaded product of resin composition
The melt-kneaded product of the resin composition of the present invention preferably has a storage modulus (E′) of 50 to 1,000 MPa, more preferably 75 to 900 MPa, still more preferably 100 to 800 MPa. When the storage elastic modulus (E') is within the above range, the self-supporting property is further improved.
In the present invention, the storage modulus (E') was measured by the method described in Examples.

Haze of the melt-kneaded product of the resin composition The haze of the melt-kneaded product of the resin composition of the present invention is preferably 0 to 10%, more preferably 0 to 7.5%, and still more preferably 0 to 5%. is.
In the present invention, haze was obtained by the following method.
The resin composition was melt-kneaded at 200° C. and 100 rpm for 3 minutes to obtain a melt-kneaded resin composition.
The resulting melt-kneaded product was compression molded at 210° C. and a pressure of 50 kgf/cm ² for 5 minutes to obtain a resin sheet with a thickness of 0.8 mm.
The haze of the obtained resin sheet was measured according to JIS K7136:2000 using a haze meter HZ-1 (manufactured by Suga Test Instruments Co., Ltd.).

Interlayer Film for Laminated Glass The interlayer film for laminated glass of the present invention may be composed only of the layer (x) containing the core-shell type polymer or the resin composition, and may be a multilayer film containing at least one layer (x). may be The multilayer film is not particularly limited, but examples thereof include a two-layer film in which the layer (x) and another layer are laminated, and a film in which another layer is arranged between the two layers (x). be done.

Examples of the other layer include a layer containing a known resin. Examples of the resin include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, polytetrafluoroethylene, acrylic resin, polyamide, polyacetal, polycarbonate, polyethylene terephthalate among polyesters, polybutylene terephthalate, cyclic polyolefin, polyphenylene sulfide, Polytetrafluoroethylene, polysulfone, polyethersulfone, polyarylate, liquid crystal polymer, polyimide and the like can be used. In addition, other layers, if necessary, plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, antiblocking agents, pigments, dyes, heat-shielding materials (for example, inorganic heat-shielding materials having infrared absorbing ability) fine particles or organic heat-shielding materials), functional inorganic compounds, and other additives.

The method for producing the interlayer film for laminated glass of the present invention is not particularly limited. The layer (x) can be obtained by forming the layer (x) by a known film forming method such as a method. Layer (x) may be used alone as an intermediate film. If necessary, the layer (x) may be laminated with other layers by press molding or the like to form a laminated interlayer film, or the layer (x) and other layers may be formed by co-extrusion to form a laminated interlayer film. may be

Among known film-forming methods, a method of producing an interlayer film for laminated glass using an extruder is preferably used. The resin temperature during extrusion is preferably 150° C. or higher, more preferably 170° C. or higher. Also, the resin temperature during extrusion is preferably 250° C. or lower, more preferably 230° C. or lower. If the resin temperature becomes too high, the resin used will decompose and there is concern about deterioration of the resin. Conversely, if the temperature is too low, the discharge from the extruder will not be stable, causing mechanical troubles. In order to remove the volatile substances efficiently, it is preferable to remove the volatile substances by reducing the pressure from the vent port of the extruder.

In addition, it is preferable that the intermediate film for laminated glass of the present invention has an uneven structure formed on its surface by a conventionally known method such as melt fracture or embossing. Conventionally known shapes can be adopted for the shape of the melt fracture and emboss. It is preferable to form an uneven structure on the surface of the interlayer film for laminated glass of the present invention, because the interlayer film for laminated glass and a base material such as glass are excellent in debubbling property when thermocompression bonding is performed.

The lower limit of the thickness of the interlayer film for laminated glass of the present invention is 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0 in order of preference (first lower limit is preferred, last lower limit is most preferred). 0.5 mm, 0.6 mm, 0.7 mm and 0.75 mm. The upper limits are 5 mm, 4 mm, 2 mm, 1.6 mm, 1.2 mm, 1.1 mm, 1 mm and 0.79 mm in order of preference (first upper limit is preferred, last upper limit is most preferred). The thickness of the interlayer for laminated glass is measured using a conventionally known method, such as a contact or non-contact thickness gauge.

The interlayer film for laminated glass of the present invention has the morphology, storage modulus (E'), and haze described for the melt-kneaded product of the resin composition of the present invention.

The glass to be laminated with the interlayer film for laminated glass of the present invention is, for example, inorganic glass such as float plate glass, polished plate glass, figured glass, wired plate glass, and heat-absorbing plate glass, as well as conventionally known glass such as polymethyl methacrylate and polycarbonate. Organic glass or the like can be used without restriction. They may be either colorless or colored. These may use 1 type and may use 2 or more types together. Also, the thickness of the glass is preferably 100 mm or less.

A laminated glass obtained by sandwiching the interlayer film for laminated glass of the present invention between two sheets of glass can be produced by a conventionally known method. Examples thereof include a method using a vacuum laminator, a method using a vacuum bag, a method using a vacuum ring, and a method using a nip roll. Moreover, after carrying out temporary press-bonding by the said method, the method of putting into an autoclave and carrying out final adhesion is also mentioned.

When using a vacuum laminator, for example, under a reduced pressure of 1×10 ⁻⁶ to 3×10 ⁻² MPa, the inorganic glass plate, the interlayer film for laminated glass, the adhesive resin layer, An organic glass plate is laminated. A method using a vacuum bag or a vacuum ring is described for example in EP 1235683 and is laminated at 100-160° C. under a pressure of about 2×10 ⁻² MPa.

As a manufacturing method using nip rolls, there is a method of performing pressure bonding at a temperature close to the flow start temperature after degassing with rolls at a temperature equal to or lower than the flow start temperature of the interlayer film for laminated glass. Specifically, for example, after heating to 30 to 70° C. with an infrared heater or the like, degassing with rolls, further heating to 50 to 120° C., and pressing with rolls can be mentioned.

When pressure bonding is performed by putting it into an autoclave after pressure bonding using the above method, the operating conditions of the autoclave process are appropriately selected depending on the thickness and structure of the laminated glass. It is preferable to treat at 100 to 160° C. for 0.5 to 3 hours.

The laminated glass preferably has excellent transparency. For example, its haze is preferably 1% or less, more preferably 0.8% or less, and even more preferably 0.5% or less. . In the present invention, haze was measured according to JIS K7136:2000 using a haze meter HZ-1 (manufactured by Suga Test Instruments Co., Ltd.).

As described above, the film obtained by molding the core-shell polymer or resin composition of the present invention is useful as an interlayer film for laminated glass. The interlayer film for laminated glass is particularly preferable as an interlayer film for laminated glass for structural materials because of its excellent adhesion to substrates such as glass, transparency, and self-supporting properties. In addition, it is suitable not only as an interlayer film for laminated glass for structural materials, but also as an interlayer film for laminated glass in various applications such as mobile bodies such as automobiles, buildings, solar cells, etc., but is limited to these applications. not a thing

Accordingly, the present invention provides a core-shell polymer in the form of an interlayer film for laminated glass, a resin composition in the form of an interlayer film for laminated glass, use of the core-shell polymer as an interlayer film for laminated glass, and a resin composition. Also includes use as an interlayer for laminated glass.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

Materials used in Examples and Comparative Examples are shown below.
(monomer)
・Methyl methacrylate: manufactured by Kuraray Co., Ltd. ・Methyl acrylate: manufactured by Tokyo Chemical Industry Co., Ltd. ・n-Butyl acrylate: manufactured by Tokyo Chemical Industry Co., Ltd. ・2-Ethylhexyl acrylate: manufactured by Tokyo Chemical Industry Co., Ltd.・n-Butyl methacrylate: manufactured by Tokyo Chemical Industry Co., Ltd. ・Allyl methacrylate: manufactured by Tokyo Chemical Industry Co., Ltd. ・Styrene: manufactured by Wako Pure Chemical Industries, Ltd. ・Methacrylic acid: manufactured by Wako Pure Chemical Industries, Ltd. ( chain transfer agent)
・ n-octyl mercaptan: manufactured by Tokyo Chemical Industry Co., Ltd. (emulsifier)
・ Sodium dodecylbenzenesulfonate: manufactured by Kao Corporation, product name “Neopelex G-15” (16% aqueous solution of active ingredient)
(Radical polymerization initiator)
・ Sodium peroxodisulfate: manufactured by Wako Pure Chemical Industries, Ltd. (dispersion medium)
・Ion-exchanged water: Ion-exchanged water with electrical conductivity of 0.08×10 ⁻⁴ S/m or less (plasticizer)
- Triethylene glycol di-2-ethylhexanoate: manufactured by Alfa Aesar

In this example, methyl methacrylate is MMA, methyl acrylate is MA, n-butyl acrylate is nBA, 2-ethylhexyl acrylate is 2EHA, n-butyl methacrylate is BMA, allyl methacrylate is ALMA, and styrene is St. , methacrylic acid is denoted as MAA, and n-octyl mercaptan is denoted as nOM.

Various analysis conditions in Examples and Comparative Examples are shown below.
[Monomer conversion]
The particles were precipitated by dropping an emulsified liquid (1 mL) sampled every hour from the start of polymerization into methanol (20 mL). After sedimentation of the particles, the solid content obtained after removing the supernatant liquid is dried under the conditions of 0.1 kPa and 60° C. using a vacuum dryer (rectangular vacuum constant temperature dryer model: DP23, manufactured by Yamato Scientific Co., Ltd.). Vacuum drying was performed until there was no change in mass.
The monomer conversion rate (% by mass) was calculated from the mass of the emulsified liquid sampled, the mass of the monomer added up to the sampling time, and the mass of the solid content after drying.

[Average dispersed particle size in emulsion at the time of production]
A mixture of the emulsified liquid (0.1 mL) obtained in Production Example and ion-exchanged water (10 mL) was analyzed for particles using a dynamic light scattering measurement device (device name: SZ-100, manufactured by Horiba, Ltd.). The particle size distribution was measured on a volume basis, and the median diameter was defined as the average dispersed particle diameter.

[Content of acetone-soluble matter]
A melt-kneaded core-shell polymer (1.25 g) obtained by the method described later was immersed in acetone (25 g) and shaken for 24 hours, then centrifuged (apparatus name: hymac CR 22GII, Hitachi The mixture was treated at 20,000 rpm for 3 hours using a machine manufactured by Koki Co., Ltd. for solid-liquid separation. The solid layer containing the swollen body was taken out and vacuum-dried under the conditions of 0.1 kPa and 70° C. using the above-mentioned vacuum dryer until there was no change in mass. did. The mass fraction of acetone-soluble matter was calculated from the following formula (1).
Mass fraction of acetone solubles = (Mc-Ma) / Mc x 100 (1)
In the formula, Mc is the mass (g) of the resin composition, and Ma is the mass (g) of the acetone-insoluble matter.

[Acid value of acetone-soluble matter]
After the acetone immersion treatment, the solid-liquid separated liquid layer was titrated with a 0.1 mol/L potassium hydroxide ethanol solution (potency (F) was standardized with 0.1N hydrochloric acid and 1% phenolphthalein solution). Then, the acid value was calculated from the neutralized amount according to the following formula.
Acid value (mmol/g) = (KOH titer (mL) x 0.1 x F)/(Mc-Ma)
wherein Mc and Ma are as defined above.

[Weight-average molecular weight of acetone-soluble matter]
After the acetone immersion treatment, the solid-liquid separated liquid layer was vacuum-dried using the vacuum dryer under conditions of 0.1 kPa and 70° C. until there was no change in mass. After 10 mg of the dried solid was dissolved in 1 mL of tetrahydrofuran, the insoluble matter was removed by filtration through a membrane filter (13JP020AN, manufactured by Toyo Roshi Kaisha, Ltd.). The filtrate was subjected to gel permeation chromatography (GPC) under the following conditions to determine the weight average molecular weight calibrated with standard polystyrene.
Apparatus: HLC-8320GPC, manufactured by Tosoh Corporation Eluent: THF
Column: TSKguardcolumn H _XL -H (6.0 mm I.D. × 4 cm), one manufactured by Tosoh Corporation, TSKgel GMH _XL (7.8 mm I.D. × 30 cm), one manufactured by Tosoh Corporation Connect two columns in series Column temperature: 40°C
Detector: RI
Liquid feed rate: 1.0 mL/min

[Average particle size of dispersed phase]
A melt-kneaded material of a core-shell type polymer obtained by the method described later was compression-molded at 210° C. and a pressure of 50 kgf/cm ² for 5 minutes to obtain a resin sheet having a thickness of 0.8 mm. The sheet was observed with an electron microscope. From the observed image, the length of the minor axis and the major axis of the dispersed phase were measured, and the dispersed particle diameter was determined by the following formula (2). The number average value of 100 dispersed phases was taken as the average particle size of the dispersed phase.
Dispersed particle diameter = (minor diameter + major diameter) / 2 (2)

[Stability in high temperature environment]
A core-shell type polymer or a melt-kneaded resin composition obtained by the method described later is compression-molded at 210° C. under a pressure of 50 kgf/cm ² for 5 minutes to obtain a resin sheet with a thickness of 0.8 mm. Ta. A test piece having a length of 40 mm and a width of 5 mm was cut out from the sheet, and the storage modulus (E′) was measured using a dynamic viscoelasticity measuring device manufactured by UBM Co., Ltd. under the conditions of a measurement temperature of 50° C. and a frequency of 1 Hz. , was used as an index of the self-supporting property of the interlayer film for laminated glass in a high-temperature environment.

[transparency]
A core-shell type polymer or a melt-kneaded resin composition obtained by the method described later is compression-molded at 210° C. under a pressure of 50 kgf/cm ² for 5 minutes to obtain a resin sheet with a thickness of 0.8 mm. Ta. The haze of the sheet was measured using a haze meter HZ-1 (manufactured by Suga Test Instruments Co., Ltd.) according to JIS K7136:2000.

[Glass adhesion]
A core-shell type polymer or a melt-kneaded resin composition obtained by the method described later is compression-molded at 210° C. under a pressure of 50 kgf/cm ² for 5 minutes to obtain a resin sheet with a thickness of 0.8 mm. Ta. The resulting resin sheet was sandwiched between two sheets of float glass having a thickness of 2.7 mm, and a vacuum laminator (manufactured by Nisshinbo Mechatronics Co., Ltd., 1522N) was used to reduce the pressure in the vacuum laminator at 100°C for 1 minute. While being held, they were pressed at 30 kPa for 5 minutes to obtain a temporary bonded body. The obtained temporarily bonded body was put into an autoclave and treated at 140° C. and 1.2 MPa for 30 minutes to obtain a laminated glass. A test sample was obtained by cutting the obtained laminated glass into a size of 25 mm×25 mm. The obtained test samples were evaluated by a compression shear strength test described in WO1999-058334. The maximum shear stress when the laminated glass was peeled was used as an index of glass adhesion.

[Slow cooling durability]
The laminated glass obtained by the above method was heated to 150°C and then slowly cooled to 23°C at a rate of 0.1°C/min. The haze of the laminated glass immediately after production and after slow cooling was measured, and the increase in haze value (ΔHaze) was used as an index of slow cooling durability.

<Production Example 1: Production of core-shell type polymer>
(Step 1')
After adding 145 g of ion-exchanged water and 1.3 g of an emulsifier (Neopelex G-15) to a dried 0.5 L pressure-resistant polymerization tank, the contents were stirred and nitrogen gas was passed through for 30 minutes to remove oxygen. processed. After raising the temperature to 70° C., an aqueous solution prepared by dissolving 0.1 g of a polymerization initiator (potassium persulfate) in 5 g of deionized water was added to the aqueous solution. After that, the monomer mixture (i′) consisting of nBA (29.46 g), St (6.25 g), and ALMA (0.21 g) was deoxidized, and then continuously added to the aqueous solution at a rate of 2 mL/min. was added to obtain an emulsion.
(Step 2')
A mixture of MMA (0.71 g), nBA (11.29 g), St (2.28 g) and ALMA (0.23 g) was deoxygenated to obtain a monomer mixture (ii'). When it was confirmed that the conversion rate of the monomer added in step 1' exceeded 99% by mass, the emulsion obtained in step 1' was added with the monomer mixture (ii') at 2 mL / min. was continuously added at a rate of to obtain an emulsion.
(Step 3')
A mixture of MMA (10.83 g), nBA (19.17 g), MAA (20 g) and nOM (0.5 g) was deoxygenated to obtain a monomer mixture (iii'). When it was confirmed that the conversion rate of the monomer added in step 2' exceeded 99% by mass, the monomer mixture (iii') was added to the emulsified liquid obtained in step 2' at a rate of 1 mL / min. was added continuously. When it was confirmed that the total monomer addition rate exceeded 99% by mass, the polymerization tank was cooled to 25° C. and the emulsion of the core-shell type polymer was taken out.
The emulsified liquid was cooled at -20°C for 24 hours to freeze, and then poured into 250 g of hot water at 80°C and stirred for 30 minutes to solidify the core-shell polymer. The solid content was collected by suction filtration, put into 500 mL of ion-exchanged water, stirred for 30 minutes, and washed with water. After repeating water washing for a total of three times, the filtered solid content was dried in a vacuum dryer at 0.1 kPa and 70° C. until there was no change in weight, to obtain a core-shell polymer CS-1.

<Production Examples 2 to 13: Production of core-shell polymer>
Each core-shell type polymer was obtained in the same manner as in Production Example 1, except that the types and amounts of the monomers used and the amount of the emulsifier used were changed as shown in Tables 1 and 2.
The core-shell polymer CS-10 (Production Example 13) corresponds to the acrylic core-shell resin ACS-1 (Production Example 4) described in Patent Document 1.

Tables 1 and 2 show the amount of each component used in the production of each core-shell type polymer.

<<Example 1>>
The core-shell polymer CS-1 was melt-kneaded for 3 minutes at a chamber temperature of 200° C. and a rotation speed of 100 rpm using Labo Plastomill (device name: 4M150, manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the contents of the chamber were taken out. After cooling, a melt-kneaded product was obtained. Various physical property evaluations were performed using the resulting melt-kneaded product. Table 3 shows the results.

<<Examples 2 to 10, Comparative Examples 1 to 3>>
A melt-kneaded product was obtained in the same manner as in Example 1, except that the core-shell type polymer was changed as shown in Tables 3 and 4. Various physical property evaluations were performed using the resulting melt-kneaded product.

<<Comparative Example 4>>
A polyvinyl butyral resin having an average degree of polymerization of about 1700 and a degree of acetalization of 69 mol% was synthesized, and 20 parts by mass of triethylene glycol di-2-ethylhexanoate was added as a plasticizer to 100 parts by mass of the polyvinyl butyral resin. Press molding was carried out at 100 kgf/cm ² and 140° C. for 10 minutes to prepare a polyvinyl butyral sheet (PVB-1) having a thickness of 0.8 mm. Various physical property evaluations were performed using the produced polyvinyl butyral sheet.

<<Comparative Example 5>>
A polyvinyl butyral resin having an average degree of polymerization of about 1700 and a degree of acetalization of 69 mol% was synthesized, and 35 parts by mass of triethylene glycol di-2-ethylhexanoate was added as a plasticizer to 100 parts by mass of the polyvinyl butyral resin. Press molding was performed at 100 Kgf/cm ² and 140° C. for 10 minutes to prepare a polyvinyl butyral sheet (PVB-2) having a thickness of 0.8 mm. Various physical property evaluations were performed using the produced polyvinyl butyral sheet.

<<Comparative Example 6>>
An ionomer resin (Himilan 1601, manufactured by DuPont) was press molded at a pressure of 100 kgf/cm ² and a temperature of 200° C. for 10 minutes to prepare an ionomer resin sheet with a thickness of 0.8 mm. Various physical property evaluations were performed using the produced ionomer resin sheet.

From the comparison of Examples 1 to 10 and Comparative Examples 4 to 6, the interlayer film containing the core-shell type polymer of the present invention is superior to conventionally used polyvinyl butyral resin films and ionomer resin films in terms of glass adhesion alone. It can be seen that the transparency and the self-sustainability in a high-temperature environment are also good.
It can be seen that the interlayer films of Examples 1 to 10 satisfying XsAs≧75 were remarkably improved in glass adhesion compared to the interlayer films of Comparative Examples 1 to 3, which did not satisfy this condition. Furthermore, it can be seen that the self-sustainability in a high-temperature environment was remarkably improved.
Thus, the film obtained by molding the core-shell polymer of the present invention or the resin composition containing the same has good glass adhesion required for an interlayer film for laminated glass, preferably good glass adhesion. In addition, it has both good transparency and good self-support.

By using the core-shell type polymer and the resin composition of the present invention, a resin film excellent in adhesiveness to glass, transparency, and self-supporting property can be obtained. The resin film is useful as an interlayer film for laminated glass, particularly as an interlayer film for laminated glass for structural materials. Furthermore, it can be suitably used not only as an interlayer film for laminated glass for structural materials, but also as an interlayer film for laminated glass in various applications such as mobile bodies such as automobiles, buildings, and solar cells. Therefore, the core-shell polymer and resin composition of the present invention are useful for producing interlayer films for laminated glass in various applications.

Claims (1)

A core-shell polymer having a core particle and a shell covering at least a portion of the core particle, wherein the content X S (% by mass) of the acetone-soluble matter with respect to the total mass of the core-shell-type polymer and the acetone- _soluble matter A resin composition containing a core-shell polymer for an interlayer film of laminated glass having an acid value A S (mmol/g) of satisfying the following relationship, wherein the content of acetone-soluble matter with respect to the total mass of the resin composition _: A resin composition containing a core-shell polymer for an interlayer film of laminated glass, wherein X _S ′ (% by mass) and an acid value A _S ′ (mmol/g) of an acetone-soluble component satisfy the following relationship.
X _S A _S ≧75
X _S 'A _S '≧75