JPWO2006080347A1 - Polymerizable composition, polymer, sheet-like molded product, laminate and production method thereof - Google Patents

Abstract

An object of this invention is to provide the polymeric composition which can obtain easily the intermediate film which has the outstanding transparency. The polymerizable composition of the present invention contains a (meth) acrylic monomer, a divalent copper ion, and an alkyl phosphate ester. The alkyl phosphate ester contains an alkyl phosphate monoester and an alkyl phosphate diester. The molar ratio of alkyl phosphate monoester / alkyl phosphate diester is 20/80 to 80/20.

Description

  The present invention relates to a polymerizable composition, a polymer, a sheet-like molded product, a laminate, and a method for producing the same.

  As an optical member for use in a window material or the like, a laminated glass having a structure in which an intermediate film made of resin or the like is sandwiched between a pair of translucent substrates made of glass or the like is known. These laminated glasses have excellent properties in terms of strength and durability, such as less damage when subjected to an impact, compared to the case where a light-transmitting substrate is used alone.

  In recent years, these laminated glasses are required to have a property of blocking infrared rays or near infrared rays (hereinafter referred to as “near infrared light”). If such a laminated glass is applied to a window material, a wall material, or the like, for example, light having a wavelength in the above-described region in sunlight, that is, entry of heat rays into the room can be suppressed. Thereby, inconveniences such as excessively high temperature in the room can be reduced.

Therefore, an attempt has been made to provide the laminated glass with a property capable of blocking near-infrared light by providing a layer made of a resin material or the like having a property of absorbing near-infrared light as an intermediate film. As a material for the interlayer film of such a laminated glass, an acrylic resin composition containing an acrylic resin, a copper ion or a metal oxide, and a phosphate group-containing compound is disclosed (for example, see Patent Document 1). ).
JP-A-9-208918

  By the way, in the laminated glass having the property of blocking near infrared light as described above, in order to ensure sufficient indoor brightness when applied to a window material or the like, a light beam having a wavelength in the visible light region is used. High translucency (translucency) is also required at the same time. The acrylic resin composition of the above prior art has sufficient translucency as an interlayer film of laminated glass, but when adjusting the resin composition, turbidity may occur depending on conditions, In some cases, a characteristic (that is, “transparency”) that allows the opposite side to be visually recognized through such a laminated glass cannot be sufficiently obtained.

  Also, recently, with the diversification of uses of laminated glass, better transparency is often required as compared with the conventional case. Therefore, the demand for materials for interlayer films that can impart such excellent transparency is rapidly increasing.

  Then, this invention is made | formed in view of such a situation, and it aims at providing the polymeric composition which can obtain easily the intermediate film which has favorable transparency compared with the former. . Another object of the present invention is to provide a polymer obtained by using such a polymerizable composition, a sheet-like molded product and an intermediate film, and a laminate comprising this intermediate film.

［式中、Ｒ^１はそれぞれ独立にアルキル基を示す。］In order to achieve the above object, the polymerizable composition of the present invention contains a (meth) acrylic monomer, a divalent copper ion, and an alkyl phosphate ester. The alkyl phosphate ester has the following general formula ( It contains an alkyl phosphate monoester represented by 1a) and an alkyl phosphate diester represented by the following general formula (1b), and the molar ratio of alkyl phosphate monoester / alkyl phosphate diester is 20 / 80 to 80/20.

[Wherein, each R ¹ independently represents an alkyl group. ]

  As a result of intensive studies by the present inventors, in the acrylic resin composition of the above prior art, depending on the combination of the acrylic resin and the phosphate group-containing compound, a phosphate group-containing compound or copper for the acrylic resin It has been found that the solubility of ions and the like may deteriorate. When the solubility is thus deteriorated, turbidity is likely to occur during the preparation of the resin composition or when an intermediate film or the like is formed from this composition, and it is difficult to obtain excellent transparency due to this. There is a tendency.

  On the other hand, the polymerizable composition of the present invention contains the alkyl phosphate ester so that the molar ratio of the monoester body and the diester body falls within a specific range as described above. The alkyl phosphate ester satisfying such conditions has a characteristic that it is very easily dissolved in the (meth) acrylic monomer together with the copper ion. Therefore, according to the polymerizable composition containing such an alkyl phosphate ester, turbidity or the like hardly occurs when an intermediate film is formed. Therefore, by using the polymerizable composition of the present invention, it becomes possible to obtain a laminated glass having excellent transparency as compared with the conventional one.

In the alkyl phosphoric acid monoester represented by the general formula (1a) and the alkyl phosphoric acid diester represented by the general formula (1b), the groups represented by R ¹ are each independently 4 to 16 carbon atoms. The alkyl group is more preferable. Such alkyl phosphoric acid (mono or di) esters are more excellent in solubility in (meth) acrylic monomers. Therefore, the polymerizable composition containing them can form an intermediate film having excellent transparency more easily.

［式中、Ｒ^２１は水素原子又はメチル基、Ｒ^２２は炭素数４〜１２のアルキル基を示す。］Moreover, the said (meth) acrylic-type monomer is more preferable in it containing 50-100 mass% of compounds represented by following General formula (2).

[Wherein, R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents an alkyl group having 4 to 12 carbon atoms. ]

  A (meth) acrylic monomer containing a compound having the above structure can form a polymer having excellent flexibility. In particular, when the content of the compound in the (meth) acrylic monomer is within the above range, the polymer has appropriate flexibility and appropriate rigidity. For this reason, the laminated glass provided with the polymerizable composition containing the (meth) acrylic monomer as an intermediate film can have not only transparency as described above but also excellent penetration resistance.

  Moreover, it is preferable that the polymerizable composition of the present invention further includes a polymerizable phosphate ester composed of a monoester body and / or a diester body of a phosphate ester having a polymerizable functional group, in addition to the above components. As described above, when an alkyl phosphate ester and a polymerizable phosphate ester are combined as a phosphate ester, the solubility in a (meth) acrylic monomer is further improved. For this reason, in the polymerizable composition having the above-described configuration, the polymer is further excellent in both flexibility and rigidity, and is extremely excellent in transparency. As a result, the laminated glass provided with the polymer composed of the polymerizable composition having the above-described structure as an intermediate film is further excellent in both transparency and penetration resistance.

  The polymerizable phosphate ester contained in the polymerizable composition of the present invention preferably has no aromatic ring. Moreover, it is more preferable that the polymerizable phosphoric acid ester has an ethylenically unsaturated group as a polymerizable functional group. As a result, the transparency and penetration resistance of the laminated glass obtained are further improved.

  The present invention also provides a polymer obtained by polymerizing the polymerizable composition of the present invention. Since such a polymer is composed of the polymerizable composition of the present invention, it has excellent near-infrared light absorbability and excellent transparency as described above.

  The present invention further provides a sheet-like molded product comprising the polymer of the present invention. Such a sheet-like molded product can be used for various applications as a film having near infrared light absorption, as well as an intermediate film for laminated glass described later.

  Moreover, the intermediate film of the present invention is suitable as an intermediate film for laminated glass, and is an intermediate film disposed between a pair of light-transmitting substrates, characterized by comprising the polymer of the present invention. It is. Such an intermediate film has excellent near-infrared light absorption and transparency as described above.

  Furthermore, this invention provides a laminated body provided with the intermediate film of the said invention. That is, the laminate of the present invention includes a pair of translucent substrates and the intermediate film of the present invention disposed between the translucent substrates. Such a laminate is applicable as so-called laminated glass. And since this laminate has an intermediate film formed from the polymerizable composition of the present invention, in addition to excellent near-infrared light absorption, it also has excellent transparency, It is extremely useful as a window material.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the polymeric composition which can obtain easily the intermediate film which has favorable transparency compared with the past. In addition, it is possible to provide a polymer, a sheet-like molded product, an intermediate film, and a laminate including the intermediate film using the polymerizable composition.

It is a figure which shows typically an example of the cross-sectional structure of a laminated glass. It is a figure which shows typically an example of the cross-section of the laminated glass which has a reflection layer.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Translucent substrate, 2 ... Intermediate film, 10 ... Laminated glass, 20 ... Laminated glass, 21 ... Translucent substrate, 22 ... Intermediate film, 23 ... Infrared reflective layer.

Hereinafter, preferred embodiments of the present invention will be described.
[Polymerizable composition]

  The polymerizable composition of this embodiment contains a (meth) acrylic monomer, a divalent copper ion, and an alkyl phosphate ester. Hereinafter, suitable examples of these components will be described.

((Meth) acrylic monomer)
First, the (meth) acrylic monomer will be described. A (meth) acrylic monomer is a monomer having one or more (meth) acrylic groups. In the present specification, the notation “(meth) acryl” collectively indicates both “acryl” and “methacryl”, and includes those including one or both of them. Further, in the present specification, “(meth) acrylate” similarly represents both “acrylate” and “methacrylate”.

  Examples of the (meth) acrylic monomer include (meth) acrylic acid or (meth) acrylic acid ester. In the (meth) acrylic acid ester, examples of the functional group bonded to the oxygen of the ester bond include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. In addition, a functional group formed by a plurality of these groups bonded through an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, or the like may be used. Furthermore, a hydroxyl group, an amino group, a thiol group, an epoxy group, or the like may be further bonded to the functional group.

  As the (meth) acrylic monomer, a (meth) acrylic acid ester is preferable. Specific examples include the compounds shown below. That is, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, n-hexyl (meth) Alkyl (meth) acrylates such as acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl ( (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isobornyl (meth) acrylate, methoxypolyethylene (meth) acrylate, phenoxy (meth) acrylate Modified (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy-1,3-di (meth) acrylate, 2,2-bis [4- (meth) acryloxyethoxyphenyl] propane, 2-hydroxy-1- (meth) acryloxy-3- (meth) acryloxypropane, trimethylolpropane tri (meth) acrylate, pentaerythritol bird Meth) acrylate, polyfunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate. These (meth) acrylic acid esters may be used alone or in combination.

Among the above-mentioned (meth) acrylic acid esters, (meth) acrylic acid alkyl esters are preferable. Among them, the functional group bonded to the oxygen of the ester bond is an alkyl group having 4 to 12 carbon atoms. Are preferable, and those having 6 to 10 alkyl groups are more preferable. That is, a compound represented by the following general formula (2) is preferable. In the formula, R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents an alkyl group having 4 to 12 carbon atoms, preferably an alkyl group having 6 to 10 carbon atoms. When the (meth) acrylic monomer contained in the polymerizable composition contains 50 to 100% by mass, preferably 60 to 100% by mass of the compound represented by the following formula (2), such (meth) acrylic monomer There exists a tendency for the softness | flexibility of the polymeric composition containing this to become favorable.

  Examples of such (meth) acrylic acid alkyl esters include methyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, and lauryl methacrylate. These alkyl (meth) acrylates can be used alone or in combination of two or more.

(Divalent copper ion)
Next, divalent copper ions will be described. Divalent copper ions are supplied into the polymerizable composition, for example, as a copper salt. Specific examples of such copper salts include copper acetate anhydrides of organic acids such as copper acetate, copper formate, copper stearate, copper benzoate, copper ethyl acetoacetate, copper pyrophosphate, copper naphthenate, copper citrate, Examples include hydrates or hydrates, or anhydrides, hydrates or hydrates of copper salts of inorganic acids such as copper chloride, copper sulfate, copper nitrate, and basic copper carbonate, or copper hydroxide. Among these, copper acetate, copper acetate monohydrate, copper benzoate, copper hydroxide, and basic copper carbonate are preferably used. In addition, these copper salts which are copper ion sources may be used independently, and may be used in multiple combination.

  Copper ions are contained in the polymerizable composition and can impart a property of absorbing near infrared light to the composition or a cured product thereof. In addition, such a copper ion is contained in combination with a phosphoric acid ester described later, so that the solubility in the polymerizable composition is extremely good. Therefore, the polymerizable composition of the present invention in which copper ions are blended in such a form has excellent transparency as well as excellent properties of absorbing near-infrared light.

(Alkyl phosphate ester)
Next, the alkyl phosphate ester will be described. The alkyl phosphate ester contains an alkyl phosphate monoester represented by the general formula (1a) and an alkyl phosphate diester represented by the general formula (1b). In addition, the two alkyl groups represented by R ¹ in the alkyl phosphate diester may be the same or different.

In the alkyl phosphate represented by the general formula (1a) or (1b), the alkyl group represented by R ¹ may be any of linear, branched and cyclic, and A combination group may be used. Among them, the alkyl group represented by ^{R 1,} preferably an alkyl group having 4 to 16 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms. In addition, R ¹ in the alkyl phosphate monoester and the alkyl phosphate diester may be the same or different.

Specifically, examples of the alkyl group represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a 2-ethylhexyl group, an isodecyl group, a lauryl group, and a stearyl group. . Of these, n-butyl group, 2-ethylhexyl group, isodecyl group, lauryl group or stearyl group is preferable, and n-butyl group, 2-ethylhexyl group, isodecyl group or lauryl group is more preferable.

  As described above, the polymerizable composition contains both the alkyl phosphate monoester represented by the general formula (1a) and the alkyl phosphate diester represented by the general formula (1b). The molar ratio of alkyl phosphate monoester / alkyl phosphate diester in the polymerizable composition is preferably in the range of 20/80 to 80/20, more preferably in the range of 30/70 to 70/30. Preferably, it is more preferable in the range of 35/65 to 62/38. When the value of this molar ratio is outside the above range, the solubility of the mixture of alkyl phosphate esters in the (meth) acrylic monomer is insufficient, and it tends to be difficult to obtain a laminated glass having sufficient transparency.

(Polymerizable phosphate ester)
The polymerizable composition according to this embodiment preferably contains a polymerizable phosphate ester. More specifically, the polymerizable phosphate ester is preferably a compound represented by the following general formula (3).

In the formula, R ³ represents an organic group having a polymerizable functional group, and s represents 1 or 2. When s is 1, two R ³ may be the same or different. One or both of the compound in which s is 1 and the compound in which s is 2 are included in the polymerizable phosphate ester compound. Here, examples of the polymerizable functional group include functional groups that can cause radical polymerization, anionic polymerization, cationic polymerization, and the like. Examples of the polymerizable functional group include a functional group containing a polymerizable unsaturated bond, an ethylenically unsaturated group is preferable, and a (meth) acryl group is more preferable. Examples of R ³ include these polymerizable functional groups themselves, or organic groups containing such polymerizable functional groups. In the latter case, R ³ may have a polymerizable functional group at either the terminal or inside.

As such a polymerizable phosphate compound, a compound represented by the following general formula (4) is preferable.

In the formula, R ⁴ is a group represented by the following general formula (5), and n is 1 or 2. However, in the following formula (5), R ⁵¹ represents a hydrogen atom or a methyl group, R ⁵² represents an alkylene group, X represents a single bond or an oxygen atom, and m is an integer of 0 to 10. In addition, when n is 1, two R < ⁴ > may be the same and may differ.

In the group represented by the general formula (5), which is R ⁴ in the compound represented by the formula (4), R ⁵² is an alkylene group. The alkylene group is preferably an alkylene group having 2 to 97 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms, and still more preferably an alkylene group having 1 to 6 carbon atoms. X is preferably an oxygen atom, and m is preferably an integer of 1 to 5. However, when X is a single bond, m is preferably 1 or more.

Especially, in the polymerizable phosphate ester represented by the general formula (4), it is more preferable that R ⁴ has a group represented by the following general formula (6).

In the group represented by the above formula (6), R ⁶² is more preferably an alkylene group having 1 to 4 carbon atoms, and p is more preferably an integer of 1 to 5. Specifically, as the polymerizable phosphoric acid ester compound represented by the general formula (4), for example, R ⁴ is a (meth) acryloyloxyethyl group, a (meth) acryloyloxybutyl group, or a (meth) acryloyl group. It is any one group selected from the group consisting of an oxypropyl group, a (meth) acryloyl poly (oxyethyl) group, a (meth) acryloyl poly (oxybutyl) group, and a (meth) acryloyl poly (oxypropyl) group. Things. In addition, the polymerizable phosphoric acid ester compound may contain alone one of those having the above-described structure, or may contain a plurality of kinds in combination.

  The polymerizable phosphate ester includes at least one of a monoester form (compound in which s = 2 in the above formula (3)) and a diester form (compound in which the s = 1 in the above formula (3)). However, it is more preferable to include both of them. By including both of these, the solubility of the polymerizable composition in the (meth) acrylic monomer and the like are further improved, and the transparency and penetration resistance of the resulting laminated glass tend to be further improved. In order to obtain such an effect better, the ratio of monoester / diester is preferably 20/80 to 80/20, more preferably 30/70 to 70/30, and more preferably 40/60 to molar ratio. 60/40 is more preferable, and 45/55 to 55/45 is particularly preferable. As a weight ratio, the ratio of monoester / diester is preferably 10/90 to 90/10, more preferably 20/80 to 80/20, still more preferably 30/70 to 70/30, and 35/65. ~ 65/35 is particularly preferred.

(Polymerizable composition)
As described above, the polymerizable composition of the present embodiment contains (meth) acrylic monomers, divalent copper ions, and alkyl phosphoric acid (mono and di) esters. In such a polymerizable composition, the divalent copper ion may exist in the state of the divalent copper ion, but the ionic bond or coordination with the alkyl phosphoric acid (mono and di) ester described above. A coordinate bond may be formed and exist in the state of an alkyl phosphate ester-copper complex.

  When a complex is formed as in the latter case, the solubility of copper ions in the (meth) acrylic monomer and its polymer is further increased, and the transparency of the polymerizable composition and the intermediate film using the same is further improved. become. This alkyl phosphate ester-copper complex may be formed in advance by, for example, mixing and reacting the above-described copper ion source and an alkyl phosphate (mono or di) ester in a predetermined solvent.

  Suitable blending amounts of these components in the polymerizable composition are as shown below. That is, the content of the (meth) acrylic monomer in the polymerizable composition is preferably 20 to 99.5% by mass, more preferably 50 to 99% by mass, and 70 to 99% by mass. Further preferred. Moreover, the content of the copper ion and the alkyl phosphate (mono and di) ester is preferably 0.5 to 80% by mass, more preferably 1 to 50% by mass, and 1 to 30% by mass. Further preferred. This content is the same when the above-mentioned alkyl phosphate ester-copper complex is formed.

  When this content is less than 0.5 parts by mass, the near-infrared light absorption performance such as an intermediate film made of the polymerizable composition tends to be insufficient as compared with the case where the content is 0.5 parts by mass or more. It is in. On the other hand, when it exceeds 45 parts by mass, it becomes difficult for copper ions and alkyl phosphoric acid (mono and di) esters or their complexes to be uniformly dissolved or dispersed in the (meth) acrylic monomer or polymer thereof, There exists a tendency for the transparency of a polymeric composition or its polymer to worsen.

  Moreover, it is more preferable that the total content of alkyl phosphates (mono and di) esters relative to divalent copper ions satisfies the following conditions. That is, when the alkyl phosphoric acid (mono and di) ester has a hydroxyl group, the total amount of the hydroxyl group / Cu (ion) is preferably 1 to 6 and 1 to 4 in terms of molar ratio. More preferably, it is still more preferable in it being 1.5-2.5. When this ratio is less than 1, the near-infrared light absorption performance and transparency of an intermediate film made of a polymerizable composition tend to be lowered. On the other hand, if it exceeds 6, the amount of hydroxyl groups that do not participate in coordination bonds or ionic bonds with copper ions becomes excessive, and the hygroscopicity tends to be excessively increased.

  Further, when the polymerizable composition further contains a polymerizable phosphate ester in addition to the above-described alkyl phosphate ester, the ratio of alkyl phosphate ester / polymerizable phosphate ester is 50/50 as a molar ratio. -95/5 is preferable, 50 / 50-90 / 10 is more preferable, 50 / 50-85 / 15 is still more preferable, 50 / 50-80 / 20 is especially preferable, and 50 / 50-57 / 43 is still more preferable. . As a weight ratio, the ratio of alkyl phosphate ester / polymerizable phosphate ester is preferably 50/50 to 95/5, more preferably 50/50 to 90/10, and still more preferably 50/50 to 85/15. 50/50 to 80/20 is more preferable. When the ratio (molar ratio or weight ratio) of alkyl phosphate ester / polymerizable phosphate ester is less than 50/50 (0/100 or more and less than 50/50), the polymer of the polymerizable composition tends to become brittle. In some cases, the penetration resistance of a laminate (such as a laminated glass) using a glass as an intermediate film becomes insufficient. On the other hand, if the ratio (molar ratio or weight ratio) of alkyl phosphate ester / polymerizable phosphate ester is greater than 95/5 (over 95/5 but not more than 100/0), solubilization promoting effect of polymerizable phosphate ester May become insufficient, and the translucency of a laminate (eg, laminated glass) using the polymer of the polymerizable composition as an intermediate film may be reduced.

(Other ingredients)
In addition to the (meth) acrylic monomer, divalent copper ion, and alkyl phosphate ester described above, the polymerizable composition of the present embodiment may contain other components in accordance with desired characteristics. . Hereinafter, other components that may be contained in the polymerizable composition will be described.

  As other components, an ultraviolet light absorber can be contained in order to further improve the stability of the polymerizable composition and the polymer to ultraviolet light. Examples of the ultraviolet light absorber include benzoate compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, oxalic acid anilide compounds, triazine compounds, and the like.

  More specifically, examples of the benzoate compound include 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, and examples of the salicylate compound include Examples thereof include phenyl salicylate and pt-butylphenyl salicylate.

  Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2 ′, 4,4′-tetrahydrobenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2′-dihydroxy-4 , 4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone-5,5′-sodium disulfonate, 2,2′-dihydroxy-5-methoxybenzophenone, 2-hydroxy-4-methacryloyl Oxyethylbenzophenone, - benzoyloxy-2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxy benzophenone.

  Examples of the benzotriazole compounds include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzo. Triazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) ) Benzotriazole, 2- (2'-hydroxy-5-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5-t-butylphenyl) benzotriazole, 2- [2'-hydroxy-3 ' -(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy -3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-5-t-octylphenyl) benzotriazole, 2- [2'-hydroxy-3', 5'-bis (Α, α-dimethoxybenzoyl) phenyl] benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-3′-dodecyl-5′-methylphenyl) benzotriazole, methyl-3- [ 3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol Like condensates of.

  Examples of cyanoacrylate compounds include ethyl-2-cyano-3,3-diphenyl acrylate and octyl-2-cyano-3,3-diphenyl acrylate. Examples of oxalic acid anilide compounds include 2-ethoxy-2 ′. -Ethyl oxalic acid bisanilide and 2-ethoxy-5-t-butyl-2'-ethyl oxalic acid bisanilide. Examples of the triazine-based compound include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol.

  The polymerizable composition can also contain a light stabilizer for further improving the stability to light. In particular, when the ultraviolet light absorber described above and this light stabilizer are used in combination, the stability to light tends to be very good. As the light stabilizer, a hindered amine light stabilizer (HALS) or a Ni-based compound can be applied.

  More specifically, HALS includes bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1 -[2- [3- (3,5-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy ] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl- 1,3,8-triazaspiro [4,5] decane-2,4-dione, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t -Butyl-4-hydroxybe Diyl) -2-n-butylmalonate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6) , 6-Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, (Mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3 , 4-Butanetetracarboxylate, Mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2,4,8, 10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, (Mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, Mixed {2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2 , 4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1 , 2,2,6,6-pentamethyl-4-piperidyl methacrylate, poly [(6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl) ] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) iminol], dimethyl succinate polymer-with-4 - Droxy-2,2,6,6-tetramethyl-1-piperidineethanol, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2 , 2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-triazine-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethylpiperidyl) butylamine polycondensate, decane And diacid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester.

  Ni-based light stabilizers include [2,2′-thio-bis (4-t-octylphenolate)]-2-ethylhexylamine-nickel (II), nickel dibutyldithiocarbonate, [2,2 '-Thio-bis (4-t-octylphenolate)]-butylamine-nickel (II) and the like.

  In addition, as a component for stabilizing the polymerizable composition, an antioxidant, a heat stabilizer and the like may be added, and as a component for adjusting the color tone, a dye, a pigment, a metal compound, etc. are added. Also good. Further, a surfactant, a flame retardant, an antistatic agent, a moisture proofing agent and the like may be added.

  In consideration of applying the polymerizable composition to an interlayer film of laminated glass, a component for adjusting adhesion to a light-transmitting substrate such as glass can be further added. Alkali metal salts, alkaline earth metal salts, silane compounds, and the like can also be added.

  Examples of the alkali metal salt or alkaline earth metal salt include alkali metal salts or alkaline earth metal salts of organic acids or inorganic acids. Examples of the organic acid include carboxylic acids such as octanoic acid, hexanoic acid, butyric acid, acetic acid and formic acid. Examples of the inorganic acid include hydrochloric acid and nitric acid. Examples of the alkali metal salt and alkaline earth metal salt include salts of potassium, sodium, calcium, magnesium and the like.

  Among the alkali metal salts or alkaline earth metal salts of organic acids or inorganic acids, alkali metal salts or alkaline earth metal salts of organic acids having 2 to 16 carbon atoms are preferred, and potassium of carboxylic acids having 2 to 16 carbon atoms. A salt or a magnesium salt is more preferable. Examples of the potassium salt and magnesium salt of a carboxylic acid having 2 to 16 carbon atoms include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutanoate, potassium 2-ethylbutanoate, and 2-ethylhexane. Magnesium acid, potassium 2-ethylhexanoate and the like are preferable. These may be used alone or in combination of two or more.

  The preferable lower limit of the compounding amount of the alkali metal salt or alkaline earth metal salt of organic acid or inorganic acid is 0.001 part by mass with respect to 100 parts by mass of the (meth) acrylic monomer, and the preferable upper limit is 0. .5 parts by weight. There exists a possibility that adhesive force may fall in a high-humidity atmosphere as this compounding quantity is less than 0.001 mass part. On the other hand, if it exceeds 0.5 parts by mass, the transparency of the interlayer film made of the polymerizable composition may be lowered. From such a viewpoint, the more preferable lower limit of the amount is 0.01 part by mass, and the more preferable upper limit is 0.2 part by mass.

  An example of the silane compound is a modified silicone oil. Examples of the modified silicone oil include epoxy-modified silicone oil, ether-modified silicone oil, ester-modified silicone oil, amine-modified silicone oil, carboxyl-modified silicone oil, and the like. These may be used independently and 2 or more types may be used together. These modified silicone oils can generally be obtained by reacting a compound to be modified with polysiloxane.

  The preferable lower limit of the molecular weight of these modified silicone oils is 800, and the upper limit is 5000. When the molecular weight of the modified silicone oil is less than 800, the localization of the silicone oil on the surface may be insufficient as compared with the case where the molecular weight is 800 or more. On the other hand, when it exceeds 5000, the compatibility with the (meth) acrylic monomer is lowered, and it may bleed out to the surface of the intermediate film to reduce the adhesive force with the glass. From such a viewpoint, the more preferable lower limit of the molecular weight of the modified silicone oil is 1500, and the more preferable upper limit is 4000.

  Moreover, the preferable lower limit of the compounding quantity of modified silicone oil is 0.01 mass part with respect to 100 mass parts of (meth) acrylic-type monomers, and an upper limit is 0.2 mass part. When the blending amount of the modified silicone oil is less than 0.01 parts by mass, the effect of preventing whitening due to moisture absorption is insufficient as compared with the case where it is 0.01 parts by mass or more, and the transparency of the interlayer film May decrease. On the other hand, when the amount exceeds 0.2 parts by mass, the compatibility with the (meth) acrylic monomer may be reduced, and the adhesive strength with the glass may be reduced by bleeding out to the surface of the intermediate film. From such a viewpoint, the more preferable lower limit of the modified silicone oil is 0.03 parts by mass, and the more preferable upper limit is 0.1 parts by mass.

Moreover, the polymeric composition may further contain metal ions other than the copper ions described above for the purpose of obtaining further characteristics. Examples of the metal ions include metal ions such as rare earth metals, iron, manganese, nickel, chromium, indium, titanium, antimony, and tin. Among these, rare earth metals have excellent absorption characteristics for light of a specific wavelength (near 580 nm or near 520 nm) due to electronic transition of f-orbitals of rare earth ions. Since these wavelength ranges match the maximum response wavelength of the photoreceptor cells of the human eyeball, the anti-glare property can be imparted to the polymerizable composition or the polymer thereof by containing a rare earth element. Examples of rare earth elements include neodymium, praseodymium and holmium.
[Polymer]

  The polymer comprising the polymerizable composition described above can be applied as a film having near-infrared light absorption by forming a sheet-like molded product as described later, and is disposed between a pair of translucent substrates. By doing so, it can be applied as an interlayer film for laminated glass having near infrared light absorption.

  Such a polymer includes, for example, a polymer having a structural unit composed of the above-mentioned (meth) acrylic monomer, a copper ion and an alkyl phosphate (mono and di) ester dissolved or dispersed in the polymer, preferably an alkyl. It contains a phosphate ester-copper complex.

The polymer having a structural unit composed of a (meth) acrylic monomer is a polymer obtained by polymerizing a (meth) acrylic monomer, and may be a homopolymer composed of only a (meth) acrylic monomer. Copolymers formed by combining monomer components may also be used. In such a polymer, the structural unit comprising a (meth) acrylic monomer is preferably 4 to 12 carbon atoms, more preferably 6 to 6 carbon atoms, as a functional group bonded to oxygen of an ester bond in each structural unit. It has 10 alkyl groups.
[Optical member]

By using the polymerizable composition described above, it is possible to obtain various optical members that are excellent in properties for blocking near-infrared light and have superior transparency as compared with the prior art. Examples of such an optical member include first and second forms shown below.
1st form: The sheet-like molding obtained by processing a polymeric composition.
2nd form: The laminated body which has a translucent board | substrate and the polymeric composition layer which consists of a polymeric composition provided adjacent to this translucent board | substrate.

(Sheet-like molded product)
First, a sheet-like molded product of the first form will be described. The sheet-like molded product is made of a polymer of the polymerizable composition. Specifically as a form of a sheet-like molded object, a sheet | seat and a film are mentioned. Here, the sheet is a thin plate having a thickness exceeding 250 μm. The film is a thin film having a thickness of 5 to 250 μm. These sheets or films can be produced using a known sheet or film forming method. Specific examples include a melt extrusion molding method, a stretch molding method, a calendar molding method, a press molding method, and a solution casting method.

(Laminate)
Next, the laminated body of a 2nd form is demonstrated. The laminate has at least a light-transmitting substrate and a polymerizable composition layer made of the polymerizable composition and provided adjacent to the light-transmitting substrate.

  In the laminate, the material constituting the translucent substrate is not particularly limited as long as it is a translucent material having visible light permeability, and can be appropriately selected according to the use of the laminate. From the viewpoint of obtaining good hardness, heat resistance, chemical resistance, durability, etc., glass or plastic is preferably used. Examples of the glass include inorganic glass, organic glass, and the like, depending on the purpose, specific functions such as colored glass, UV-cut glass having a wavelength dependency on transmittance, or glass having a heat shielding function such as green glass. It is also possible to use glass having Examples of the plastic include polycarbonate, acrylonitrile-styrene copolymer, polymethyl methacrylate, vinyl chloride resin, polystyrene, polyester, polyolefin, norbornene resin, and the like. Similarly to glass, those having a specific function may be appropriately selected and used. When there are a plurality of light-transmitting substrates, each substrate may be composed of the same type of material or may be composed of different materials.

  Such a laminated body can be manufactured as follows, for example. That is, it can be manufactured by first forming a sheet or film that is the above-described sheet-like molded product, and then laminating the sheet or the like and a translucent substrate. Examples of a method for bonding them together include a means for bonding by pressurization or pressure reduction such as a press method, a multi-roll method, and a pressure reduction method, a means for bonding by heating with an autoclave, or a combination of these.

  In addition to the method of pasting sheets formed in advance in this way, a method of directly forming a polymerizable composition layer on a light-transmitting substrate can also be applied. As such a method, for example, the polymerizable composition is dissolved and / or dispersed in an appropriate solvent to form a coating agent, and after the solution is applied to a light-transmitting substrate, the solvent is evaporated to obtain a light-transmitting property. Examples thereof include a method of forming a thin film, a covering or a thin layer made of a polymerizable composition on a substrate. The thin film formed in this way is called a coating. When a polymerizable composition layer is formed using such a method, for the purpose of improving the flatness of the layer, the above-mentioned solubilizing agents such as various surfactants such as a leveling agent and an antifoaming agent are described above. You may add in a coating agent.

(Laminated glass)
A laminated body is not limited to what is provided with the translucent board | substrate and polymeric composition layer which were mentioned above one by one, You may provide these layers with two or more. Specifically, what is provided with a pair of translucent board | substrates and the intermediate film (polymerizable composition layer) which consists of the said polymeric composition arrange | positioned between this translucent board | substrate is mentioned. Such a laminated body is called a so-called laminated glass, and has a characteristic of excellent strength and the like, and can be suitably used as a window material or the like.

  Here, with reference to FIG. 1, the laminated glass of suitable embodiment is demonstrated.

  Drawing 1 is a figure showing typically an example of the section structure of the laminated glass of an embodiment. A laminated glass 10 shown in FIG. 1 includes a pair of translucent substrates 1 and an intermediate film 2 sandwiched between the pair of translucent substrates 1. The intermediate film 2 is a polymer made of the polymerizable composition of the above-described embodiment. Moreover, as the translucent board | substrate 1, the thing similar to the laminated body mentioned above is applicable.

  In the laminated glass 10 having such a structure, for example, a sheet-like molded product made of the above-described polymerizable composition is sandwiched between a pair of translucent substrates 1, and this is preliminarily pressed to leave the air remaining between the layers. After removing, it can be manufactured by a method in which these are pressure-bonded and brought into close contact with each other. In addition, a pair of translucent substrates can be arranged at a predetermined interval, and a liquid polymerizable composition before polymerization can be introduced therebetween, and then the polymerizable composition can be polymerized. .

  In addition, like the former, when manufacturing the laminated glass 10 by the method of pinching | interposing a sheet-like molded product, the sheet | seat shaped material used as the intermediate film 2 joins the said sheets at the time of the storage, and becomes a lump shape. In other words, it is required that a so-called blocking phenomenon does not occur and that the deaeration property in the pre-bonding is good. When these requirements are satisfied, workability when superimposing the translucent substrate 1 and a sheet is improved, and translucency due to bubbles generated due to insufficient deaeration, for example. Can be prevented.

  From the viewpoint of application to a window material or the like, the laminated glass 10 is required to be excellent in visible light transmittance, that is, in the property of transmitting light in the visible light region, in addition to the property of blocking near-infrared light. In order to obtain excellent visible light transmissivity, in addition to the good translucency of the intermediate film 2 itself, air bubbles that cause turbidity are formed between the translucent substrate 1 and the intermediate film 2. Is preferably not left as much as possible. The generation of bubbles by the intermediate film 2 depends on the type of polymerizable composition and physical properties such as viscoelasticity, but tends to be greatly influenced by the surface shape of the intermediate film 2.

  As one of means for reducing the generation of bubbles by changing the surface shape, a method using an intermediate film 2 having a large number of minute irregularities called emboss on the surface is known. According to the embossed intermediate film 2, the deaeration property in the above-described precompression bonding process and the like is good, and the remaining bubbles are extremely small and are easily taken into the intermediate film 2. As a result, the laminated glass 10 has few bubbles remaining between the translucent substrate 1 and the intermediate film 2, and the translucency deterioration due to the bubbles is extremely small.

  As the form of embossing, for example, various uneven patterns composed of a large number of convex portions and a large number of concave portions for these convex portions, various uneven patterns composed of a large number of convex strips and a large number of concave grooves for these convex strips, There are embossed shapes with various values for various form factors such as roughness, placement, size, and the like.

  As these embossments, for example, those described in Japanese Patent Laid-Open No. 6-198809, the size of the convex portion is changed, and the size and arrangement thereof are defined, and those described in Japanese Patent Laid-Open No. 9-40444 are disclosed. Surface roughness of 20-50 μm, described in JP-A-9-295839, arranged so that the ridges intersect, or described in JP-A-2003-48762, The thing which formed the smaller convex part on the main convex part is mentioned. In addition, as a method for applying an embossed shape, for example, Japanese Patent Application Publication No. 2003-528749 describes a method using a melt fracture generated during resin molding. In addition, JP-A-2002-505221, JP-A-9-502755, and the like describe methods using crosslinked PVB particles and a nucleating agent.

  In addition, as another characteristic recently required for the laminated glass 10, sound insulation is cited. According to the laminated glass having excellent sound insulation, for example, when used for a window material, the influence of ambient noise and the like can be reduced, and the indoor environment can be further improved. In general, the sound insulation performance is shown as a transmission loss amount corresponding to a change in frequency, and the transmission loss amount is defined by JISA 4708 at a constant value according to the sound insulation grade at 500 Hz or more.

  A glass plate frequently used as a light-transmitting substrate in general laminated glass has a tendency that its sound insulation performance is significantly lowered due to a coincidence effect in a frequency region centered on 2000 Hz. Here, the coincidence effect means that when a sound wave is incident on a glass plate, the transverse wave propagates through the glass plate due to the rigidity and inertia of the glass plate, and the transverse wave and the incident sound resonate. This is a phenomenon that occurs. Therefore, in general laminated glass, it is difficult to avoid a decrease in sound insulation performance in a frequency region centered on 2000 Hz, and improvement of this point is demanded.

  In this regard, it is known from the equal loudness curve that human hearing exhibits a very good sensitivity in the range of 1000 to 6000 Hz compared to other frequency regions. Accordingly, it is important to eliminate the drop in the sound insulation performance due to the coincidence effect described above in order to improve the sound insulation performance. From such a viewpoint, in order to improve the sound insulation performance of the laminated glass 10, it is necessary to alleviate the decrease in the sound insulation performance due to the coincidence effect and to prevent the minimum portion of the transmission loss due to the coincidence effect from being lowered.

  Here, as a method of imparting sound insulation to the laminated glass 10, a method of increasing the mass of the laminated glass 10, a method of compounding the glass to be the translucent substrate 1, a method of subdividing this glass area, There is a method of improving the glass plate supporting means. In addition, it is known that the sound insulation performance depends on the dynamic viscoelasticity of the intermediate film 2 and may be particularly affected by the loss tangent, which is the ratio between the storage elastic modulus and the loss elastic modulus. Therefore, the sound insulation performance of the laminated glass 10 can be enhanced also by controlling this value.

  As a means for controlling the value of the loss tangent of the intermediate film 2, for example, a method using a resin film having a specific degree of polymerization, a method for defining a resin structure as described in JP-A-4-2317443, Examples thereof include a method for defining the amount of plasticizer in the resin as described in JP-A-2001-220183. It is also known that the sound insulation performance of the laminated glass 10 can be enhanced over a wide temperature range by combining two or more different resins to form an intermediate film. For example, a method of blending a plurality of types of resins described in JP-A-2001-206742, and a method of laminating a plurality of types of resins described in JP-A-2001-206741 and JP-A-2001-226152. And a method described in Japanese Patent Application Laid-Open No. 2001-192243 for imparting a deflection to the amount of plasticizer in the intermediate film. By adopting these techniques as appropriate and implementing a combination of means such as modification of the resin structure, addition of a plasticizer, combination of two or more resins, etc., the loss tangent of the resin material on which the intermediate film 2 is to be formed It becomes possible to control the value satisfactorily, and it becomes easy to obtain a desired sound insulation.

  Furthermore, it is preferable that the laminated glass 10 can further exhibit heat shielding properties other than blocking near-infrared light. As a method for improving the heat shielding property of the laminated glass 10, there is a method in which the intermediate film 2 further contains oxide fine particles having a heat shielding function. As such a method, for example, methods described in JP 2001-206743 A, JP 2001-261383 A, JP 2001-302289 A, and the like can be applied. Further, the heat shielding property can be improved by further providing a layer containing oxide fine particles or the like in the laminated glass.

  Examples of the oxide fine particles include tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), and aluminum-doped zinc oxide (AZO). Since the intermediate film 2 containing the oxide fine particles tends to have low translucency, a method of defining the particle diameter of the oxide fine particles so that sufficient translucency can be obtained (see FIG. No. 2002-293583), a method for increasing the dispersibility of oxide fine particles, and the like may be applied. As a method for enhancing the dispersibility of oxide fine particles as in the latter case, known fine particle dispersion techniques such as mechanically dispersing the fine particles or using a dispersant can be applied.

  As a method for improving the heat shielding property of the laminated glass, in addition to the method of containing the oxide fine particles described above, for example, a method of containing an organic dye / pigment having a heat shielding function, or a light transmitting property having a heat shielding performance A method using a substrate is also included. Examples of the method of containing an organic dye / pigment having a heat shielding function include methods described in JP-A-7-157344 and JP-A-319271. Examples of the organic dye / pigment include phthalocyanine, anthraquinone, naphthoquinone, cyanine, naphthalocyanine, pyrrole, imonium, dithiol, and mercaptonaphthol.

  Moreover, as a translucent board | substrate which has heat insulation performance, glass (for example, green glass etc.) containing transition metals, such as Fe described in Unexamined-Japanese-Patent No. 2001-151539, for example, Unexamined-Japanese-Patent No. 2001-261384 Examples thereof include a glass plate having a multilayer coating of metals and metal oxides described in Japanese Patent Laid-Open No. 2001-226148.

  Thus, the laminated glass 10 of embodiment mentioned above interrupts | blocks the near-infrared light which is a heat ray, when the near-infrared-light absorption material contained in the intermediate film 2 absorbs the light ray of a near-infrared light area | region. The laminated glass 10 reflects near-infrared light in addition to the intermediate film 2 having near-infrared light absorption for the purpose of further improving near-infrared light blocking characteristics. You may further provide the layer (infrared reflective layer) which has a characteristic. Such an infrared reflective layer can be introduced at an arbitrary position of the laminated glass.

  FIG. 2 is a diagram schematically illustrating an example of a cross-sectional structure of a laminated glass having a reflective layer. The laminated glass 20 has a structure including a translucent substrate 21, an intermediate film 22, an infrared reflection layer 23, and a translucent substrate 21 in this order. The same thing as the translucent board | substrate 1 and the intermediate film 2 in the laminated glass 10 mentioned above can be applied to the translucent board | substrate 21 and the intermediate film 22. FIG.

  Examples of the infrared reflecting layer 23 include a layer made of a metal or a metal oxide. Specific examples include simple metals such as gold, silver, copper, tin, aluminum, nickel, palladium, silicon, chromium, titanium, indium, and antimony, alloys, mixtures, and oxides. Such an infrared reflective layer 23 can be formed, for example, by vapor-depositing a metal or a metal oxide on the surface on which the layer 23 is to be formed. In addition, as the infrared reflection layer 23, special table Hei 09-506837, special table 2000-506082, special table 2000-506084, special table 2004-525403, special table 2003-515754, JP-A-2002-231038, special table 2004 A polymer multilayer film that reflects light at a specific wavelength by using light interference as shown in −503402 may be applied.

  Here, when the infrared reflective layer 23 is formed between the translucent substrate 21 and the intermediate film 22 as in the laminated glass 20 described above, the infrared reflective layer 23 and a layer adjacent thereto (for example, an intermediate layer) Adhesiveness with the film 22) may decrease. In this case, for example, when the laminated glass 20 is broken, the translucent substrate 21 is easily peeled off and scattered, which causes a problem in terms of safety.

  Therefore, in order to avoid such a decrease in adhesiveness, a layer capable of improving the adhesive force between the intermediate film 22 and the infrared reflection layer 23 can be further provided. Examples of means for adjusting the adhesive force between the two layers include the following methods. That is, when the intermediate film 22 and the infrared reflection layer 23 are adjacent to each other like the laminated glass 20, a layer made of polyvinyl acetal having an acetal degree higher than that of the intermediate film 22 (see Japanese Patent Application Laid-Open No. Hei 7). -187726, JP-A-8-337446), a method of providing a layer made of PVB having a predetermined ratio of acetoxy groups (JP-A-8-337445), or a predetermined silicone oil A method of providing a layer (publication of JP-A-7-314609) can be employed. In the laminated glass, the infrared reflection layer is not necessarily provided between the translucent substrate and the intermediate film as described above, and a plurality of resin layers are provided between the translucent substrates. When formed, the form provided between these layers may be sufficient.

  In this way, in the laminated glass, in addition to the intermediate film having near infrared light absorptivity, by further providing a reflective layer having near infrared light reflectivity, the effect of both layers allows for the laminated glass. Extremely excellent near-infrared light blocking characteristics can be imparted. Moreover, if the method for improving the adhesiveness between the infrared reflection layer and the intermediate film (infrared absorption layer) as described above is adopted, laminated glass having superior strength in addition to the near infrared light blocking property Can also be obtained.

  In a laminated body such as laminated glass having the above-described structure, when light containing a heat ray component such as sunlight is incident, the near-infrared light absorbability that the intermediate film made of the polymerizable composition of the present invention develops is reduced. Heat rays in the infrared light region (wavelength of about 700 to 1200 nm) are blocked. In general, light in this wavelength range tends to feel the irritating and exciting heat that burns the skin, but the light transmitted through the above-mentioned laminate is blocked by such near-infrared light. Will be. Therefore, if this laminated body is used for a window material etc., the temperature rise indoors or indoors can be suppressed.

  The polymerizable composition forming the interlayer film of the laminate (laminated glass) contains an alkyl phosphate ester having a predetermined monoester / diester ratio as described above. The alkyl phosphate ester satisfying such conditions is dissolved or dispersed well in the (meth) acrylic monomer contained in the polymerizable composition together with the copper ion or complexed with the copper ion. obtain. For this reason, the intermediate film or the like made of the polymerizable composition of the present invention is extremely unlikely to cause turbidity due to poor compatibility between the phosphate group-containing compound and the resin component, and transmits light in the visible light region. Property (that is, translucency) is very good. As a result, a laminated body (laminated glass) provided with such an intermediate film is excellent in both near-infrared light absorption and translucency, and is extremely effective in applications such as window materials.

  Thus, since the laminated body (laminated glass) of the present invention has excellent near-infrared light blocking performance, it is a building material (a building member) for taking in natural light such as sunlight or other external light. For example, window materials for automobiles, ships, aircraft or train (railway) vehicles, canopy materials for passages such as arcades, curtains, canopies for carports and garages, solarium windows or wall materials, show windows, Showcase window materials, tents or window materials, blinds, roofing materials such as stationary and temporary housing, skylights and other window materials, coating materials for painted surfaces such as road signs, sunshade materials such as parasols, and other heat shielding Can be suitably used for various members that require the above.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.
[Preparation of Composition Containing Alkyl Phosphate Ester and Copper Ion]

(Preparation Example 1)
First, as alkyl phosphate ester, 2.76 g of 2-ethylhexyl phosphate ester mixture (manufactured by Tokyo Chemical Industry Co., Ltd.) having a molar ratio of phosphoric acid monoester component and phosphoric acid diester component of 50:50 and di-2- Ethylhexyl phosphate ester (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.24 g was mixed to prepare 2-ethylhexyl phosphate ester in which the ratio of the phosphoric acid monoester component and the phosphoric acid diester component was 30:70 in molar ratio.

  Next, 2.18 g of copper acetate monohydrate and 15 g of toluene were added to the obtained 2-ethylhexyl phosphate to perform deacetic acid reflux. And after filtering the solution after reaction, toluene was distilled off and the composition containing an alkyl phosphate ester and a copper ion was obtained.

(Preparation Example 2)
As the alkyl phosphate ester, 50.00 g of a 2-ethylhexyl phosphate ester mixture having a molar ratio of the phosphate monoester component and the phosphate diester component of 50:50 is prepared, and copper acetate monohydrate is added thereto. After adding 27.8 g and 150 g of toluene, deacetic acid reflux was performed. Next, after filtering the solution after reaction, toluene was distilled off and the composition containing an alkyl phosphate ester and a copper ion was obtained.

(Preparation Example 3)
As the alkyl phosphate ester, 2-ethylhexyl phosphate ester in which the ratio of the phosphate monoester component and the phosphate diester component was 60:40 in molar ratio was prepared. Next, a composition containing an alkyl phosphate ester and copper ions in the same manner as in Preparation Example 1, except that 3.16 g of copper acetate monohydrate was used for 5.00 g of this 2-ethylhexyl phosphate ester. Got.

(Preparation Example 4)
As the alkyl phosphate ester, 2-ethylhexyl phosphate ester in which the ratio of the phosphate monoester component to the phosphate diester component was 65:35 in molar ratio was prepared. Next, a composition containing an alkyl phosphate ester and copper ions in the same manner as in Preparation Example 1, except that 3.34 g of copper acetate monohydrate was used for 5.00 g of this 2-ethylhexyl phosphate ester. Got.

(Preparation Example 5)
As the alkyl phosphate ester, a 2-ethylhexyl phosphate ester in which the ratio of the phosphate monoester component to the phosphate diester component was 70:30 in molar ratio was prepared. Next, a composition containing an alkyl phosphate ester and copper ions in the same manner as in Preparation Example 1, except that 3.51 g of copper acetate monohydrate was used for 5.00 g of this 2-ethylhexyl phosphate ester. Got.

(Preparation Example 6)
As the alkyl phosphate ester, a 2-ethylhexyl phosphate ester in which the ratio of the phosphate monoester component and the phosphate diester component was 80:20 in molar ratio was prepared. Next, a composition containing an alkyl phosphate ester and copper ions in the same manner as in Preparation Example 1 except that 3.84 g of copper acetate monohydrate was used for 5.00 g of this 2-ethylhexyl phosphate ester. Got.

(Preparation Example 7)
As the alkyl phosphate ester, 5.00 g of an n-butyl phosphate ester mixture (manufactured by Tokyo Chemical Industry Co., Ltd.) having a molar ratio of the phosphoric monoester component and the phosphoric diester component of 50:50 was prepared. Next, a composition containing an alkyl phosphate ester and copper ions was obtained in the same manner as in Preparation Example 1 except that 2.37 g of copper acetate monohydrate was used for this n-butyl phosphate ester mixture.

(Preparation Example 8)
As an alkyl phosphate ester, 5.00 g of an isodecyl phosphate ester mixture (trade name AP-10, manufactured by Daihachi Chemical Co., Ltd.) in which the ratio of the phosphoric acid monoester component to the phosphoric diester component is 50:50 in molar ratio is prepared. did. Next, a composition containing an alkyl phosphate ester and copper ions was obtained in the same manner as in Preparation Example 1 except that 2.43 g of copper acetate monohydrate was used for this isodecyl phosphate mixture.

(Preparation Example 9)
As the alkyl phosphate ester, 5.00 g of a lauryl phosphate ester mixture (trade name JP-512, manufactured by Johoku Chemical Co., Ltd.) having a molar ratio of a phosphoric monoester component and a phosphoric diester component of 50:50 was prepared. . Next, a composition containing an alkyl phosphate ester and copper ions was obtained in the same manner as in Preparation Example 1 except that 2.14 g of copper acetate monohydrate was used for the lauryl phosphate ester mixture.

(Comparative Preparation Example 1)
As the alkyl phosphate ester, 66.6 g of di-2-ethylhexyl phosphate ester was prepared. Then, alkyl diphosphate and copper ions are contained in the same manner as in Preparation Example 1 except that 20.0 g of copper acetate monohydrate and 180 g of toluene are added to the di-2-ethylhexyl phosphate. A composition was obtained.

(Comparative Preparation Example 2)
As alkyl phosphoric acid ester, 1.00 g of 2-ethylhexyl phosphoric acid ester mixture in which the ratio of phosphoric acid monoester component and phosphoric diester component is 50:50 in molar ratio and 4.00 g of di-2-ethylhexyl phosphoric acid ester Were mixed to prepare 2-ethylhexyl phosphate having a molar ratio of the phosphoric monoester component and the phosphoric diester component of 10:90. A composition containing an alkyl phosphate ester and copper ions was obtained in the same manner as in Preparation Example 1, except that 1.76 g of copper acetate monohydrate was used for the obtained 2-ethylhexyl phosphate ester. .

(Comparative Preparation Example 3)
A 2-methoxypropyl phosphate ester in which the ratio of the phosphoric acid monoester component and the phosphoric acid diester component was 50:50 in molar ratio was prepared. A composition containing a phosphate ester and copper ions was obtained in the same manner as in Preparation Example 1, except that 5 g of copper acetate monohydrate was used with respect to 5 g of this 2-methoxypropyl phosphate ester.

(Comparative Preparation Example 4)
A 2-methoxypropyl phosphate having a molar ratio of the phosphoric acid monoester component and the phosphoric acid diester component of 75:25 was prepared. A composition containing a phosphate ester and copper ions was obtained in the same manner as in Preparation Example 1, except that 5.04 g of copper acetate monohydrate was used for 5 g of this 2-methoxypropyl phosphate ester.
[Preparation of polymerizable composition]

(Examples 1-9 and Comparative Examples 1-4)
A composition containing 0.5 g of an alkyl phosphate ester and copper ions obtained in Preparation Examples 1 to 9 and Comparative Preparation Examples 1 to 4 was dissolved in 9.5 g of 2-ethylhexyl methacrylate (manufactured by Tokyo Chemical Industry). The polymerizable composition of 1-9 and Comparative Examples 1-4 was prepared. In addition, the case where the composition of Preparation Examples 1-9 was used corresponds to Examples 1-9, respectively, and the case where the composition of Comparative Preparation Examples 1-4 was used corresponds to Comparative Examples 1-4.

(Example 10)
The polymerizable composition of Example 10 is obtained by dissolving 0.5 g of the composition containing the alkyl phosphate ester and copper ion obtained in Preparation Example 2 in 9.5 g of n-butyl methacrylate (manufactured by Tokyo Chemical Industry). It was.

(Example 11)
A polymerizable composition of Example 11 was obtained in the same manner as Example 10 except that isodecyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of n-butyl methacrylate.

(Example 12)
A polymerizable composition of Example 12 was obtained in the same manner as Example 10 except that lauryl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of n-butyl methacrylate.

(Example 13)
A polymerizable composition of Example 13 was obtained in the same manner as Example 10 except that cyclohexyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of n-butyl methacrylate.

(Example 14)
Example 10 except that the composition containing the alkyl phosphate ester and copper ion obtained in Preparation Example 8 was used in place of the composition containing the alkyl phosphate ester and copper ion obtained in Preparation Example 2. In the same manner as described above, a polymerizable composition of Example 14 was obtained.
[Evaluation of transparency of polymer]

(Production of laminated glass)
Laminated glasses were prepared as shown below using the polymerizable compositions of Examples 1 to 14 and Comparative Examples 1 to 4, respectively.

  First, 0.02 g of α-methylstyrene and 0.10 g of t-butylperoxyneodecanoate were added to the polymerizable composition and well stirred. In addition, two float plate glasses having a thickness of 3 mm and a size of 75 mm × 75 mm were prepared and held in a state of being separated by 1 mm so as to face each other. Sealed with.

  Then, after the composition after stirring was injected from the injection port, the injection port was closed with a polyester tape. Next, the glass plate in a state where the polymerizable composition was poured was left in an oven, and the oven temperature was kept at 40 ° C. for 8 hours. Thereafter, the temperature in the oven is increased to 110 ° C. over 3 hours, and then maintained at the same temperature for 3 hours to polymerize and cure the polymerizable composition, whereby an intermediate composed of a polymer of the polymerizable composition. A film was formed. After cooling, the polyester tape attached to the side surface was peeled off to obtain a laminated glass.

(Measurement of haze)
The haze at the time of completion of the laminated glass obtained using each of the polymerizable compositions of Examples 1 to 14 and Comparative Examples 1 to 4 was measured by a method based on JIS K 7136. The obtained results are shown in Table 1. The lower the haze, the better the transparency of the laminated glass. In Table 1, the molar ratio of monoester / diester in the alkyl phosphate ester (2-methoxypropyl phosphate ester in Comparative Examples 3 and 4) used in each polymerizable composition (in the table, (Expressed as “mono / di ratio”), carbon number of alkyl group of alkyl phosphate ester (expressed as “C (phosphoric acid)” in the table), and oxygen in ester bond of (meth) acrylic monomer The number of carbon atoms of the alkyl group bonded to (indicated in the table as “C (monomer)”) is also shown.

From Table 1, the laminated glass of Examples 1-14 obtained using the polymerizable composition in which the molar ratio of alkyl phosphate monoester / alkyl phosphate diester was within a suitable range is the value of this ratio. The haze value was significantly smaller than the laminated glass obtained using the polymerizable compositions of Comparative Examples 1 and 2 that were outside the preferred range. Moreover, the laminated glass of Comparative Example 3 or 4 obtained by using a polymerizable composition using 2-methoxypropyl phosphate as a phosphate ester has a large haze value as compared with the laminated glass of Examples. It was big.
[Preparation of Composition Containing Alkyl Phosphate Ester and Copper Ion]

(Preparation Example 10)
419.6 g of 2-ethylhexyl methacrylate was added to 199.7 g of copper acetate monohydrate, and the ratio of the phosphoric acid monoester component and the phosphoric diester component as an alkyl phosphate was 50 by molar ratio. After adding 355.1 g of 2-ethylhexyl phosphate ester mixture (manufactured by Tokyo Chemical Industry Co., Ltd.) of 50, the mixture was heated at 100 ° C. for 1 hour. The mixed solution after heating is evaporated under reduced pressure to distill off acetic acid and water, and a mixture of a composition containing an alkyl phosphate ester and copper ions and 2-ethylhexyl methacrylate (mixing ratio 50:50 (mass) Ratio)) 833.2 g was obtained.

(Comparative Preparation Example 5)
1200 g of toluene was added to 199.7 g of copper acetate monohydrate, and further, 644.8 g of di-2-ethylhexyl phosphate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as an alkyl phosphate to this mixture. And heated for 1 hour to obtain a solution. Acetic acid and water were distilled off while refluxing the heated mixed solution. Then, toluene was distilled off by evaporation under reduced pressure to obtain 706.4 g of a composition containing an alkyl phosphate ester and copper ions.
[Preparation of composition containing polymerizable phosphate ester and copper ion]

(Preparation Example 11)
400 g of methyl methacrylate was added to 199.7 g of copper acetate monohydrate, and the ratio of the phosphoric acid monoester component and the phosphoric diester component was 50:50 as a polymerizable phosphoric ester in a molar ratio. After adding 354.9 g of a certain 2-methacryloyloxyethyl phosphate ester mixture (manufactured by Kyoeisha Chemical Co., Ltd.), the mixture was heated at 100 ° C. for 1 hour. By evaporating the mixed solution after heating under reduced pressure, acetic acid, water and methyl methacrylate were distilled off to obtain 416.5 g of a composition containing a polymerizable phosphate ester and copper ions.
[Preparation of polymerizable composition and production of laminated glass]

First, one or more of the compositions containing each phosphate ester and copper ion obtained in Preparation Example 10, Preparation Example 11 and Comparative Adjustment Example 5 are listed in Table 2 together with (meth) acrylic monomers and other components. The polymerizable compositions of Examples 15 to 17 and Comparative Examples 5 to 7 were prepared by mixing so as to achieve the blending ratio shown.

  The abbreviations in Table 2 are as follows. That is, MMA represents methyl methacrylate, 2EH-MA represents 2-ethylhexyl methacrylate, nBu-A represents n-butyl acrylate, and 2EH-A represents 2-ethylhexyl acrylate. P-ND is perbutyl ND (radical generator, 70% solution of t-butyl peroxyneodecanoate, manufactured by NOF Corporation), and α-MeSt is α-methylstyrene (polymerization rate modifier). Each is shown.

Next, the laminated glass was produced with the method shown below using the polymeric composition of Examples 15-17 and Comparative Examples 5-7. That is, first, two float plate glasses having a thickness of 3 mm and a size of 170 mm × 170 mm were prepared and held in a state of being separated by 1 mm so as to face each other. Both side surfaces were sealed with a polyester tape except for the inlet. Then, after injecting the polymerizable composition from the injection port, the injection port was closed with a polyester tape. The glass plate in a state where the polymerizable composition was poured was allowed to stand in an oven, and the oven temperature was maintained at 40 ° C. for 8 hours. Thereafter, the temperature in the oven is increased to 110 ° C. over 3 hours, and then maintained at the same temperature for 3 hours to polymerize and cure the polymerizable composition, whereby an intermediate composed of a polymer of the polymerizable composition. A film was formed. After cooling, the polyester tape attached to the side surface was peeled off to obtain a laminated glass.
[Evaluation of transparency and penetration resistance]

  According to the method shown below, the haze measurement of each laminated glass obtained using the polymerizable composition of Examples 15-17 and Comparative Examples 5-7 and evaluation of penetration resistance were performed. The obtained results are shown in Table 3. Table 3 also shows the molar ratio of the monoester / diester in the alkyl phosphate used in each polymerizable composition (in the table, expressed as “mono / di ratio”).

(Measurement of haze)
The haze at the time of completion | finish of the laminated glass obtained using the polymerizable composition of Examples 15-17 and Comparative Examples 5-7 was measured by the method based on JISK7136, respectively. The lower the haze, the better the transparency of the laminated glass.

(Evaluation of penetration resistance)
The laminated glass obtained using the polymerizable compositions of Examples 15 to 17 and Comparative Examples 5 to 7 was sandwiched between two stainless steel frames each having an outer frame size of 230 mm × 230 mm and an inner frame size of 150 mm × 150 mm, and the horizontal Fixed to. A chrome steel ball having a diameter of 63.5 mm and a mass of 1044 g is dropped on each of the laminated glasses fixed in this manner from the height of 80 cm to the vicinity of the center of the laminated glass, and is arranged between the glasses when the glass is broken. The degree of breakage of the intermediate film was confirmed visually.

  From Table 3, the laminated glass obtained using the polymerizable compositions of Examples 15 to 17 has a low haze of 3.0 or less and excellent transparency, and also has no penetration resistance because it did not break. It turned out to be excellent. On the other hand, the laminated glass obtained with the polymerizable composition of Comparative Example 5 that did not contain an alkyl phosphate ester was found to be inferior in penetration resistance due to breakage although haze was low. Moreover, the laminated glass obtained by the polymerizable composition of Comparative Example 6 or 7 in which a polymerizable phosphate ester and a diester of an alkyl phosphate ester are combined has a high haze and transparency without causing breakage. It was insufficient.

Claims (11)

A (meth) acrylic monomer, a divalent copper ion, and an alkyl phosphate ester,
The alkyl phosphate ester contains an alkyl phosphate monoester represented by the following general formula (1a) and an alkyl phosphate diester represented by the following general formula (1b).
The molar ratio of the alkyl phosphate monoester / the alkyl phosphate diester is 20/80 to 80/20,
A polymerizable composition characterized by the above.

[Wherein, each R ¹ independently represents an alkyl group. ] The polymerizable composition according to claim 1, wherein each R ¹ is independently an alkyl group having 4 to 16 carbon atoms. The polymerizable composition according to claim 1, wherein the (meth) acrylic monomer contains 50 to 100% by mass of a compound represented by the following general formula (2).

[Wherein, R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents an alkyl group having 4 to 12 carbon atoms. ] The polymerizable composition according to any one of claims 1 to 3, further comprising a polymerizable phosphate ester comprising a monoester and / or diester of a phosphate ester having a polymerizable functional group. . The polymerizable composition according to claim 4, wherein the polymerizable phosphate ester does not have an aromatic ring. The polymerizable composition according to claim 4 or 5, wherein the polymerizable phosphate ester has an ethylenically unsaturated group as the polymerizable functional group. A polymer obtained by polymerizing the polymerizable composition according to any one of claims 1 to 6. A sheet-like molded product comprising the polymer according to claim 7. An intermediate film disposed between a pair of translucent substrates,
An intermediate film comprising the polymer according to claim 7. A pair of translucent substrates;
An intermediate film made of the polymer according to claim 7, disposed between the translucent substrates,
A laminate comprising: Arranging a pair of translucent substrates at a predetermined interval; and
Injecting the polymerizable composition according to any one of claims 1 to 6 between the pair of translucent substrates;
Polymerizing the polymerizable composition;
The manufacturing method of the laminated body which has.

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