JP2015124298A - Adhesive for glass, sealing agent for glass, glass molded product and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide adhesive for glass with a little color and superior in transparency, and sealant for glass, glass molding and laminated glass using the adhesive.SOLUTION: Provided are adhesive for glass containing propylene homopolymer satisfying following (1)-(3), and sealant for glass, glass molding and laminated glass using the adhesive: (1) mesopentad fraction [mmmm] is 20-80%; (2) weight average molecular weight (Mw) is 10,000-500,000; and (3) molecular weight distribution (Mw/Mn) is not more than 2.5.

Description

  The present invention relates to a glass adhesive, and a glass sealing agent, a glass molded article and a laminated glass using the same.

Conventionally, a laminated glass formed by sandwiching an intermediate layer made of a transparent adhesive between glass plates is used for a glass used for an automobile, particularly a windshield. The laminated glass has improved penetration resistance as a whole due to the presence of the intermediate film, and the glass pieces are less likely to scatter when subjected to an impact from the outside.
As an adhesive for glass for forming such an interlayer film, Patent Document 1 discloses the use of an ethylene vinyl acetate copolymer, and Patent Document 2 uses a functionalized polyolefin. It is disclosed.

JP 2002-187746 A Special table 2012-200283 gazette

Among them, Patent Document 2 describes that poly-α-olefin is used as an adhesive for glass, but the poly-α-olefin obtained by the production method disclosed herein is colored brown. There was a problem that the coloration was increased when the material was easily melted by heating. In addition, since a low molecular weight component is contained in a large amount due to its component structure, there is a problem that irregularities on the surface cause irregular or streaky appearance defects at the interface with the glass.
Accordingly, the present invention provides an adhesive for glass that is less colored, excellent in transparency, and hardly causes poor appearance at the interface with glass, and a sealing agent for glass, a glass molded product, and a laminated glass using the same. With the goal.

As a result of intensive studies, the present inventor has found that the above problem can be solved by using a propylene homopolymer having specific stereoregularity, molecular weight and molecular weight distribution as an adhesive for glass.
That is, the present invention provides the following.
1. A glass adhesive comprising a propylene homopolymer satisfying the following (1) to (3):
(1) Mesopentad fraction [mmmm] is 20 to 80%.
(2) The weight average molecular weight (Mw) is 10,000 to 500,000.
(3) Molecular weight distribution (Mw / Mn) is 2.5 or less.
2. A glass sealing agent comprising the glass adhesive according to 1 above.
3. A glass molded article bonded using the glass adhesive described in 1 above.
4). A laminated glass comprising a glass plate and a glass plate or a plastic sheet sandwiching an intermediate film, wherein the intermediate film is made of the glass adhesive described in 1 above.

  According to the present invention, there are provided an adhesive for glass that is less colored, excellent in transparency, and hardly causes poor appearance at the interface with glass, and a sealing agent for glass, a glass molded article, and a laminated glass using the same. be able to.

  The glass adhesive of the present invention comprises a propylene homopolymer described later.

[Propylene homopolymer]
The propylene homopolymer satisfies the following (1) to (3), preferably further satisfies the following (4) and (5).
(1) Mesopentad fraction [mmmm] is 20 to 80 mol%.
(2) The weight average molecular weight (Mw) is 10,000 to 500,000.
(3) Molecular weight distribution (Mw / Mn) is 2.5 or less.
(4) The racemic meso racemic meso pentad fraction [rmrm] is less than 2.5 mol%.
(5) Melting | fusing point (Tm-D) is 0-140 degreeC.

In the present invention, the mesopentad fraction [mmmm] and the racemic meso-racemic mesopentad fraction [rmrm] are the same as those proposed by A. Zambelli in “Macromolecules, 6, 925 (1973)”. The meso fraction and the racemic meso racemic meso fraction in the pentad unit in the polypropylene molecular chain measured by the methyl group signal in the ¹³ C-NMR spectrum.

^{The 13} C-NMR spectrum was measured using the following apparatus and conditions.
Device: JEOL Ltd., JNM-EX400 type ¹³ C-NMR device Method: Proton complete decoupling method Concentration: 220 mg / ml
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

<Calculation formula>
M = m / S × 100
R = γ / S × 100
S = Pββ + Pαβ + Pαγ
S: Signal intensity of side chain methyl carbon atoms of all propylene units Pββ: 19.8 to 22.5 ppm
Pαβ: 18.0 to 17.5 ppm
Pαγ: 17.5 to 17.1 ppm
γ: Racemic pentad chain: 20.7 to 20.3 ppm
m: Mesopentad chain: 21.7-22.5 ppm

Moreover, in this invention, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are things of polystyrene conversion measured with the following apparatus and conditions, and molecular weight distribution (Mw / Mn) is these weight average molecular weights. It is a value calculated from (Mw) and number average molecular weight (Mn).
<GPC measurement device>
Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
<Measurement conditions>
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

(1) Mesopentad fraction [mmmm]
The propylene homopolymer has a mesopentad fraction [mmmm] of 20 to 80 mol%. When [mmmm] is less than 20 mol%, the cohesive force is poor. Moreover, when [mmmm] is more than 80 mol%, the wettability with respect to the glass which is a to-be-adhered body will deteriorate, and adhesive force will fall. From such a viewpoint, the mesopentad fraction [mmmm] is preferably 30 to 75 mol%, more preferably 35 to 70 mol%. By adjusting the monomer concentration and reaction pressure, it is possible to control the mesopentad fraction [mmmm] of the propylene homopolymer.

(2) Weight average molecular weight (Mw)
The propylene polymer has a weight average molecular weight of 10,000 to 500,000. When the weight average molecular weight is less than 10,000, the cohesive force is weak. Moreover, since a viscosity will become high too high that a weight average molecular weight exceeds 500,000, it is inferior to coating property. From such a viewpoint, the weight average molecular weight of the propylene-based polymer is preferably 15,000 to 400,000, more preferably 20,000 to 300,000. The weight average molecular weight of the propylene polymer can be controlled by appropriately adjusting the polymerization conditions (propylene pressure, polymerization time, etc.).

(3) Molecular weight distribution (Mw / Mn)
The propylene homopolymer has a molecular weight distribution (Mw / Mn) of 2.5 or less. When the molecular weight distribution exceeds 2.5, the coatability is inferior, and coloring occurs due to an increase in low molecular weight components. From such a viewpoint, the molecular weight distribution is preferably 2.4 or less, more preferably 2.2 or less. The molecular weight distribution (Mw / Mn) of the propylene homopolymer can be controlled to 2.5 or less by using a metallocene catalyst.

(4) Racemic meso racemic meso pentad fraction [rmrm]
The propylene homopolymer preferably has a racemic meso racemic meso pentad fraction [rmrm] of less than 2.5 mol%. If the racemic meso racemic meso pentad fraction [rmrm] is less than 2.5 mol%, good cohesive strength is exhibited. From such a viewpoint, the racemic meso racemic meso pentad fraction [rmrm] is more preferably less than 2.4 mol%, and even more preferably less than 2.2 mol%. The racemic meso racemic meso pentad fraction [rmrm] can be controlled by appropriately changing the catalyst using a metallocene catalyst as shown in the present specification.

(5) Melting point (Tm-D)
The melting point (Tm-D) of the propylene homopolymer is preferably 0 to 140 ° C, more preferably 20 to 130 ° C, and still more preferably 40 to 120 ° C, from the viewpoints of coatability and moldability.
In the present invention, a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer Co., Ltd.) is used, and 10 mg of a sample is held at −10 ° C. for 5 minutes in a nitrogen atmosphere and then heated at 10 ° C./min. The peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by the above is defined as the melting point (Tm-D). It is possible to control the melting point by adjusting the monomer concentration and the reaction pressure.

(Propylene homopolymer production method)
Examples of the method for producing the propylene homopolymer include a method for producing a propylene homopolymer by homopolymerizing propylene using a metallocene catalyst.
Examples of the metallocene catalyst include JP-A-58-19309, JP-A-61-130314, JP-A-3-163088, JP-A-4-300787, JP-A-4-21694, and special tables. Transition metal compounds having one or two ligands such as a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and the like, as described in JP-A-1-502036 Examples thereof include a catalyst obtained by combining a transition metal compound whose ligand is geometrically controlled and a promoter.

In the method for producing the propylene homopolymer, the metallocene catalyst is preferably a transition metal compound in which a ligand forms a crosslinked structure via a crosslinking group, and in particular, two crosslinking groups. More preferred is a method using a metallocene catalyst obtained by combining a transition metal compound forming a crosslinked structure via a promoter and a promoter.
Specifically, (A) the transition metal compound represented by the general formula (I), and (B) (B-1) the ion reacting with the transition metal compound of the component (A) or a derivative thereof And (B-2) a method of homopolymerizing propylene in the presence of a polymerization catalyst containing a component selected from aluminoxane.

[In the formula, M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series. E ¹ and E ² are substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group, phosphide group, hydrocarbon group and silicon-containing group, respectively. A ligand selected from the above, which forms a crosslinked structure via A ¹ and A ² , and they may be the same or different from each other. X represents a σ-bonding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked with other X, E ¹ , E ² or Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different and may be cross-linked with other Y, E ¹ , E ² or X. A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, germanium containing group, a tin-containing group, -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 -Or -AlR ^1- , wherein R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different from each other. Also good. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]

  In the above general formula (I), M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium. And lanthanoid metals. Among these, from the viewpoint of olefin polymerization activity, a metal element belonging to Group 4 of the periodic table is preferable, and titanium, zirconium and hafnium are particularly preferable.

E ¹ and E ² are respectively substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N <), phosphine group (—P <), Hydrocarbon group [>CR-,> C <] and silicon-containing group [>SiR-,> Si <] (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group) A ligand selected from among (A), and a crosslinked structure is formed via A ¹ and A ² . E ¹ and E ² may be the same as or different from each other. As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable. Examples of the substituent include a hydrocarbon group having 1 to 20 carbon atoms and a silicon-containing group.

X represents a σ-bonding ligand, and when there are a plurality of X, the plurality of Xs may be the same or different and may be cross-linked with other X, E ¹ , E ² or Y. . Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, carbon Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms.

  Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl groups, ethyl groups, propyl groups, butyl groups, hexyl groups, cyclohexyl groups, octyl groups and other alkyl groups; vinyl groups, propenyl groups, cyclohexenyl groups, etc. An arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group Group, anthracenyl group, aryl group such as phenanthonyl group, and the like. Of these, alkyl groups such as methyl group, ethyl group, and propyl group, and aryl groups such as phenyl group are preferable.

Examples of the alkoxy group having 1 to 20 carbon atoms include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, a phenylmethoxy group, and a phenylethoxy group. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group. Examples of the amide group having 1 to 20 carbon atoms include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, a dicyclohexylamide group, and a methylethylamide group, a divinylamide group, and a dipropenylamide group. Alkenylamide groups such as dicyclohexenylamide group; arylalkylamide groups such as dibenzylamide group, phenylethylamide group and phenylpropylamide group; arylamide groups such as diphenylamide group and dinaphthylamide group.
Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group, Trihydrocarbon-substituted silyl groups such as tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group and trinaphthylsilyl group; hydrocarbons such as trimethylsilyl ether group A substituted silyl ether group; a silicon-substituted alkyl group such as a trimethylsilylmethyl group; a silicon-substituted aryl group such as a trimethylsilylphenyl group; Of these, a trimethylsilylmethyl group, a phenyldimethylsilylethyl group, and the like are preferable.

  Examples of the phosphide group having 1 to 20 carbon atoms include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group; vinyl sulfide group, propenyl sulfide Group, alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, Ethyl phenyl sulfide group, propyl phenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide group, Tiger Se Nils sulfide group, an aryl sulfide groups such as a phenanthridine Nils sulfide group.

Examples of the sulfide group having 1 to 20 carbon atoms include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group; vinyl sulfide group, propenyl sulfide Group, alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, Ethyl phenyl sulfide group, propyl phenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide group, Tiger Se Nils sulfide group, an aryl sulfide groups such as a phenanthridine Nils sulfide group.
Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, thearoyl group, oleoyl group and other alkyl acyl groups, benzoyl group, toluoyl group, salicyloyl group, Examples thereof include arylacyl groups such as cinnamoyl group, naphthoyl group and phthaloyl group, and oxalyl group, malonyl group and succinyl group respectively derived from dicarboxylic acid such as oxalic acid, malonic acid and succinic acid.

On the other hand, Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.
Examples of the amine include amines having 1 to 20 carbon atoms, specifically, methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclohexylamine. Alkylamines such as methylethylamine; alkenylamines such as vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine, dicyclohexenylamine; arylalkylamines such as phenylamine, phenylethylamine, phenylpropylamine; An arylamine such as naphthylamine can be mentioned.

  Examples of ethers include aliphatic single ether compounds such as methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, and isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, Aliphatic hybrid ether compounds such as methyl-n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl-n-amyl ether, ethyl isoamyl ether; vinyl ether, allyl ether, methyl Aliphatic unsaturated ether compounds such as vinyl ether, methyl allyl ether, ethyl vinyl ether, ethyl allyl ether; anisole Aromatic ether compounds such as phenetol, phenyl ether, benzyl ether, phenyl benzyl ether, α-naphthyl ether, β-naphthyl ether, and cyclic ether compounds such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, and dioxane. Can be mentioned.

  Examples of phosphines include phosphines having 1 to 20 carbon atoms. Specific examples include monohydrocarbon-substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, and octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dicyclohexyl Dihydrocarbon-substituted phosphines such as phosphine and dioctylphosphine; alkyl phosphines such as trihydrocarbon-substituted phosphines such as trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, tricyclohexylphosphine, and trioctylphosphine; vinyl Monoalkenes such as phosphine, propenylphosphine, cyclohexenylphosphine, etc. Dialkenylphosphine in which two alkenyls are substituted for phosphine and phosphine hydrogen atoms; Trialkenylphosphine in which three alkenyls are substituted for phosphine hydrogens; Arylalkylphosphine such as benzylphosphine, phenylethylphosphine, phenylpropylphosphine; Diarylalkylphosphine or aryldialkylphosphine having three hydrogen atoms substituted with aryl or alkenyl; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, propylphenylphosphine, biphenylphosphine, naphthylphosphine, methylnaphthyl Phosphine, anthracenyl phosphine, phenanthenyl phosphine; phosphine water Atom alkyl aryl two substituted di (alkylaryl) phosphine; arylphosphine such as a hydrogen atom of phosphine alkylaryl three substituted with tri (alkylaryl) phosphine. Examples of the thioethers include the aforementioned sulfides.

Next, A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group. Group, germanium-containing group, tin-containing group, —O—, —CO—, —S—, —SO ₂ —, —Se—, —NR ¹ —, —PR ¹ —, —P (O) R ¹ —, —BR ¹ — or —AlR ¹ —, wherein R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, May be different. Examples of such a cross-linking group include those represented by the following general formula (II).

（Ｄは炭素、ケイ素又はスズ、Ｒ²及びＲ³はそれぞれ水素原子又は炭素数１〜２０の炭化水素基で、それらは互いに同一でも異なっていてもよく、また互いに結合して環構造を形成していてもよい。ｅは１〜４の整数を示す。）

(D is carbon, silicon or tin, R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other, and are bonded to each other to form a ring structure. (E represents an integer of 1 to 4)

Specific examples thereof include methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH ₂ ═C =), dimethylsilylene group, diphenyl. Examples thereof include a silylene group, a methylphenylsilylene group, a dimethylgermylene group, a dimethylstannylene group, a tetramethyldisilylene group, and a diphenyldisilylene group. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.

  q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.

As specific examples of the transition metal compound represented by the general formula (I), specific examples described in WO02 / 16450 are also preferable examples in the present invention.
More preferable specific examples include (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene). (Indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride and the like can be mentioned.

Next, as the component (B-1) in the component (B), any component can be used as long as it can form an ionic complex by reacting with the transition metal compound of the component (A). Although it can be used, what is represented by the following general formula (III), (IV) can be used conveniently.
([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b (III)
([L ² ] ^{k +} ) _a ([Z] ⁻ ) _b (IV)
(However, L ² is ^{M 2, R 11 R 12 M} 3, R 13 3 C or R ¹⁴ M ^3.)

In the general formulas (III) and (IV), L ¹ represents a Lewis base, and [Z] ⁻ represents a non-coordinating anion [Z ¹ ] ⁻ and [Z ² ] ⁻ .
[Z ¹ ] ⁻ represents an anion having a plurality of groups bonded to the element, that is, [M ¹ G ¹ G ² ... G ^f ] ⁻ . Here, M ¹ represents a group 5-15 element of the periodic table, preferably a group 13-15 element of the periodic table. G ^{1 to} G ^f are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, Aryloxy group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, acyloxy group having 1 to 20 carbon atoms , An organic metalloid group, or a C2-C20 heteroatom-containing hydrocarbon group. Two or more of G ^{1 to} G ^f may form a ring. f represents an integer of [(valence of central metal M ¹ ) +1].
[Z ^{2] -,} the acid logarithm of the reciprocal of the dissociation constant (pKa) -10 below Bronsted acid alone or in blend combination of slashed.nsted acids and Lewis acids conjugate base or commonly acids defined as super acid, The conjugate base of In addition, a Lewis base may be coordinated.
R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group.
R ¹¹ and R ¹² each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, or a fluorenyl group.
R ¹³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group.
R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. k is an ionic valence of [L ¹ −R ¹⁰ ], [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² includes elements in groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents elements 7 to 12 in the periodic table.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Amines such as pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine, thioethers such as tetrahydrothiophene, benzoic acid Examples thereof include esters such as ethyl acid, and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ¹¹ and R ¹² include cyclopentadienyl group and methylcyclopentadienyl group. , Ethylcyclopentadienyl group, pentamethylcyclopentadienyl group, and the like. Specific examples of R ¹³ include a phenyl group, p-tolyl group, p-methoxyphenyl group, and the like. Specific examples of R ¹⁴ include tetraphenylporphine, phthalocyanine, allyl, methallyl, and the like. . Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, I _{3 and the} like. Specific examples of M ³ include Mn, Fe, Co, Ni, Zn. Etc.

In [Z ¹ ] ⁻ , that is, [M ¹ G ¹ G ² ... G ^f ], specific examples of M ¹ include B, Al, Si, P, As, Sb, etc., preferably B and Al are Can be mentioned. Specific examples of G ¹ and G ^{2 to} G ^f include a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group, a phenoxy group as an alkoxy group or an aryloxy group, and the like. Hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t -Butylphenyl group, 3,5-dimethylphenyl group, etc., fluorine, chlorine, bromine, iodine as halogen atoms, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group as heteroatom-containing hydrocarbon groups, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoro Oromechiru) phenyl group, such as bis (trimethylsilyl) methyl group, pentamethyl antimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexyl antimony group, such as diphenyl boron and the like.

The non-coordinating anion i.e. pKa of -10 or less Bronsted acid alone or Bronsted acid and the conjugate base of a combination of a Lewis acid [Z ^{2] -} trifluoromethanesulfonic acid anion (CF ₃ SO Specific examples of ₃ ) ^- , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ) ^- , trifluoroacetate anion (CF ₃ CO ₂ ) ^- , Hexafluoroantimony anion (SbF ₆ ) ^- , fluorosulfonate anion (FSO ₃ ) ^- , chlorosulfonate anion (ClSO ₃ ) ^- , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ^- , Fluorosulfonate anion / 5 Fluoride arsenic ^{_{(FSO 3 / AsF 5) -}} , trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.

Specific examples of such an ionic compound that reacts with the transition metal compound of the component (A) to form an ionic complex, ie, the component compound (B-1), include triethylammonium tetraphenylborate, tetraphenylboric acid. Tri-n-butylammonium, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenyl tetraphenylborate Ammonium, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetrapheny Methyl borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) Tetra-n-butylammonium borate, tetraethylammonium tetrakis (pentafluorophenyl) tetraethylammonium borate, benzyl (tri-n-butyl) ammonium borate, tetrakis (pentafluorophenyl) methyldiphenylammonium borate, tetrakis (pentafluoro) Phenyl) triphenyl (methyl) ammonium borate, tetrakis (pentafluorophenyl) methylanilinium borate, Dimethylanilinium trakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) methyl borate (4-cyanopyridinium), tetrakis (pentafluorophenyl) triphenylphosphonium borate, tetrakis [ Bis (3,5-ditrifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, tetrapheni Silver ruborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) ) Decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) trityl borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Teoraphenylporphyrin manganese borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, tri Examples thereof include silver fluoromethanesulfonate.
(B-1) may be used alone or in combination of two or more.

（式中、Ｒ¹⁵は炭素数１〜２０、好ましくは１〜１２のアルキル基，アルケニル基，アリール基，アリールアルキル基などの炭化水素基あるいはハロゲン原子を示し、ｗは平均重合度を示し、通常２〜５０、好ましくは２〜４０の整数である。なお、各Ｒ¹⁵は同じでも異なっていてもよい。）
で示される鎖状アルミノキサン、及び一般式（ＶＩ）

（式中、Ｒ¹⁵及びｗは前記一般式（Ｖ）におけるものと同じである。）
で示される環状アルミノキサンを挙げることができる。 On the other hand, as the aluminoxane of the component (B-2), the general formula (V)

(Wherein R ¹⁵ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms or a halogen atom, and w represents an average degree of polymerization. Usually, it is an integer of 2 to 50, preferably 2 to 40. Note that each R ¹⁵ may be the same or different.
A chain aluminoxane represented by the general formula (VI)

(In the formula, R ¹⁵ and w are the same as those in the general formula (V).)
The cyclic aluminoxane shown by these can be mentioned.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means is not particularly limited and may be reacted according to a known method. For example, (i) a method in which an organoaluminum compound is dissolved in an organic solvent and contacting it with water, (ii) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (iii) a metal There are a method of reacting water adsorbed on a salt or the like with water adsorbed on an inorganic or organic substance with an organoaluminum compound, and (iv) a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum and further reacting with water. . The aluminoxane may be insoluble in toluene.
These aluminoxanes may be used alone or in combination of two or more.

  The use ratio of (A) catalyst component to (B) catalyst component is preferably 10: 1 to 1: 100 in molar ratio when (B-1) compound is used as (B) catalyst component. Preferably, the range of 2: 1 to 1:10 is desirable, and if it deviates from the above range, the catalyst cost per unit mass polymer increases, which is not practical. When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000. When deviating from this range, the catalyst cost per unit mass polymer becomes high, which is not practical. Moreover, (B-1) and (B-2) can also be used individually or in combination of 2 or more types as a catalyst component (B).

The catalyst for polymerization in the above production method can use an organoaluminum compound as the component (C) in addition to the components (A) and (B).
Here, as the organoaluminum compound of the component (C), the general formula (VII)
R ¹⁶ _v AlJ _3-v (VII)
[Wherein, R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms. (It is an integer)
The compound shown by these is used.
Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride. , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.
These organoaluminum compounds may be used alone or in combination of two or more.

In the said manufacturing method, a preliminary contact can also be performed using (A) component, (B) component, and (C) component mentioned above. The preliminary contact can be performed by, for example, bringing the component (A) into contact with the component (B), but the method is not particularly limited, and a known method can be used. These preliminary contacts are effective in reducing the catalyst cost, such as improving the catalyst activity and reducing the proportion of the (B) component that is the promoter. Further, by bringing the component (A) and the component (B-2) into contact with each other, an effect of improving the molecular weight can be seen together with the above effect. The preliminary contact temperature is usually -20 ° C to 200 ° C, preferably -10 ° C to 150 ° C, more preferably 0 ° C to 80 ° C. In the preliminary contact, an aliphatic hydrocarbon, an aromatic hydrocarbon, or the like can be used as the inert hydrocarbon of the solvent. Particularly preferred among these are aliphatic hydrocarbons.
The use ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2000, still more preferably 1:10 to 1 in terms of molar ratio. : The range of 1000 is desirable. By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if the amount is too large, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

In the present invention, at least one of the catalyst components can be supported on a suitable carrier and used. The type of the carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. In particular, inorganic oxide carriers or other inorganic carriers are preferable.
Specific examples of the inorganic oxide carrier include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and mixtures thereof. Examples thereof include silica alumina, zeolite, ferrite, and glass fiber. Of these, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like.
On the other hand, as a carrier other than the above, a magnesium compound represented by the general formula MgR ¹⁷ _X X ¹ _y typified by MgCl ₂ , Mg (OC ₂ H ₅ ) ₂ or the like, or a complex salt thereof can be used. Here, R ¹⁷ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2, y is 0 to 2, and x + y = 2. Each R ¹⁷ and each X ¹ may be the same or different.
Examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, poly 1-butene, substituted polystyrene, and polyarylate, starch, and carbon.
As the carrier used in the above production method, MgCl ₂ , MgCl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) ₂ , SiO ₂ , Al ₂ O _{3 and the} like are preferable. The properties of the carrier vary depending on the type and production method, but the average particle size is usually 1 to 300 μm, preferably 10 to 200 μm, more preferably 20 to 100 μm.
If the particle size is small, fine powder in the polymer increases, and if the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of the hopper.
The specific surface area of the carrier is usually 1 to 1000 m ² / g, preferably 50 to 500 m ² / g, and the pore volume is usually 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g. is there.
When either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and pore volume can be determined from the volume of nitrogen gas adsorbed according to the BET method, for example.
Further, when the carrier is an inorganic oxide carrier, it is usually desirable to use it after baking at 150 to 1000 ° C, preferably 200 to 800 ° C.

When at least one kind of catalyst component is supported on the carrier, it is desirable to support at least one of (A) catalyst component and (B) catalyst component, preferably both (A) catalyst component and (B) catalyst component. .
The method for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, (i) at least one of the component (A) and the component (B) is mixed with the carrier. A method, (ii) a method in which a support is treated with an organoaluminum compound or a halogen-containing silicon compound and then mixed with at least one of the component (A) and the component (B) in an inert solvent, (iii) the support and (A) A method of reacting the component and / or the component (B) with the organoaluminum compound or the halogen-containing silicon compound, (iv) after the component (A) or the component (B) is supported on the carrier, the component (B) or (A ) A method of mixing with the component, (v) a method of mixing the contact reaction product of the component (A) with the component (B) with the carrier, and (vi) a carrier during the contact reaction of the component (A) with the component (B). Coexist Or the like can be used that way.
In the above reactions (iv), (v) and (vi), an organoaluminum compound (C) can also be added.

In the present invention, when contacting the (A), (B), and (C), the catalyst may be prepared by irradiating elastic waves. Examples of the elastic wave include a normal sound wave, particularly preferably an ultrasonic wave. Specifically, an ultrasonic wave having a frequency of 1 to 1000 kHz, preferably an ultrasonic wave having a frequency of 10 to 500 kHz can be mentioned.
The catalyst thus obtained may be used for polymerization after removing the solvent once and taking out as a solid, or may be used for polymerization as it is.
Moreover, in this invention, a catalyst can be produced | generated by performing the carrying | support operation to the support | carrier of at least one of (A) component and (B) component within a polymerization system. For example, at least one of the component (A) and the component (B), a carrier, and, if necessary, the organoaluminum compound of the component (C) are added, and an olefin such as ethylene is added at normal pressure to 2 MPa (gauge), and -20 to 200 A method of preliminarily polymerizing at about 1 minute to 2 hours to form catalyst particles can be used.
In the present invention, the use ratio of the component (B-1) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 in terms of mass ratio. -2) The use ratio of the component and the carrier is preferably 1: 0.5 to 1: 1000, more preferably 1: 1 to 1:50 in terms of mass ratio. When using 2 or more types as a component (B), it is desirable that the use ratio of each component (B) and the carrier is within the above range in terms of mass ratio. In addition, the ratio of the component (A) to the carrier used is, by mass ratio, preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500.
If the ratio of component (B) [component (B-1) or component (B-2)] and the carrier, or component (A) and carrier is outside the above range, the activity may decrease. is there. The average particle size of the polymerization catalyst of the present invention thus prepared is usually 2 to 200 μm, preferably 10 to 150 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g. , Preferably it is 50-500 m < ² > / g. If the average particle size is less than 2 μm, fine powder in the polymer may increase, and if it exceeds 200 μm, coarse particles in the polymer may increase. When the specific surface area is less than 20 m ² / g, the activity may decrease, and when it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. In the catalyst of the present invention, the amount of transition metal in 100 g of the support is preferably 0.05 to 10 g, particularly preferably 0.1 to 2 g. If the amount of transition metal is outside the above range, the activity may be lowered.
In this way, a polymer having an industrially advantageous high bulk density and an excellent particle size distribution can be obtained by supporting it on a carrier.

The propylene homopolymer can be produced by homopolymerizing propylene using the polymerization catalyst described above.
In this case, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, or a suspension polymerization method may be used. A polymerization method is particularly preferred. The solution polymerization method is particularly preferable from the viewpoint of easy control of the reaction.
About polymerization conditions, superposition | polymerization temperature is -100-250 degreeC normally, Preferably it is -50-200 degreeC, More preferably, it is 0-130 degreeC. The ratio of the catalyst to the reaction raw material is preferably 10 ⁵ to 10 ⁸ , particularly preferably 10 ⁶ to 10 ^7, with respect to the raw material monomer / the component (A) (molar ratio). Furthermore, the polymerization time is usually 5 minutes to 10 hours, the reaction pressure is preferably normal pressure to 3 MPa (gauge), more preferably normal pressure to 2.5 MPa (gauge), and even more preferably normal pressure to 2 MPa (gauge). . By adjusting the reaction pressure, the mesopentad fraction [mmmm] can be controlled.
Examples of the method for adjusting the molecular weight of the polymer include selection of the type, amount used, and polymerization temperature of each catalyst component, and further polymerization in the presence of hydrogen.

When using a polymerization solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane, and octane , Halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Moreover, you may use monomers, such as an alpha olefin, as a solvent. Depending on the polymerization method, it can be carried out without solvent.
In the polymerization, prepolymerization can be performed using the polymerization catalyst. The prepolymerization can be performed, for example, by bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited, and a known method can be used. The olefin used for the prepolymerization is not particularly limited, and examples thereof include ethylene, an α-olefin having 3 to 20 carbon atoms, or a mixture thereof. It is advantageous to use the same olefin as that used in the polymerization. It is.
Moreover, prepolymerization temperature is -20-200 degreeC normally, Preferably it is -10-130 degreeC, More preferably, it is 0-80 degreeC. In the prepolymerization, an aliphatic hydrocarbon, aromatic hydrocarbon, monomer or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferred. Moreover, you may perform prepolymerization without a solvent.
In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product is 0.2 deciliter / g or more, particularly 0.5 deciliter / g or more, per 1 mmol of transition metal component in the catalyst. It is desirable to adjust the conditions so that the amount of the prepolymerized product is 1 to 10000 g, particularly 10 to 1000 g.

As the propylene homopolymer, an unmodified one is preferable from the viewpoint of preventing coloration or the like, but in the range that does not adversely affect the effects of the present invention, even a functionalized propylene homopolymer with functionalized molecular ends may be used. Good.
Examples of the functional group possessed by the functionalized propylene homopolymer include a hydroxyl group, an epoxy group, an alkoxysilyl group, an alkylsilyl group, a carboxyl group, an amino group, and an isocyanate group.

The glass adhesive of the present invention may be composed only of the propylene homopolymer, but may further contain an ethylene polymer, a tackifying resin, a wax and the like.
The glass adhesive of the present invention preferably contains 50% by mass or more of the propylene homopolymer, more preferably 70% by mass or more, and even more preferably 90% by mass or more.

(Ethylene polymer)
Specific examples of the ethylene-based polymer include polyethylene and a copolymer of ethylene and an olefin having 3 to 10 carbon atoms. From the viewpoint of adhesiveness, an ethylene-α-olefin copolymer is preferable. Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene. , 1-octadecene, 1-eicosene and the like. In this invention, 1 type, or 2 or more types can be used among these. Among these α-olefins, 1-octene is preferable. The ethylene-α-olefin copolymer used in the present invention contains 50 to 90% by mass of structural units derived from ethylene and 10 to 50% by mass of structural units derived from α-olefins from the viewpoint of adhesiveness. Those are preferred.

  The melting point of the ethylene polymer is preferably 60 to 100 ° C., more preferably 60 to 75 ° C., from the viewpoint of heat-resistant creep resistance. The melting point of the ethylene polymer can be measured by differential scanning calorimetry.

  Examples of commercially available ethylene polymers used in the present invention include Exact series (manufactured by Exxon Mobil), Affinity polymer series (manufactured by Dow Chemical), and more preferably, Affinity GA1950 (Dow Chemical). (All are trade names).

(Tackifying resin)
The glass adhesive of the present invention may contain a tackifying resin.
Examples of the tackifying resin include solid, semi-solid, and liquid materials at room temperature made of rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, and the like. You may use these individually or in combination of 2 or more types. In the present invention, it is preferable to use a hydrogenated product in consideration of compatibility with the base polymer. Among them, a hydride of a petroleum resin excellent in thermal stability is more preferable, and a hydride of an aliphatic or aliphatic hydrocarbon-based copolymer hydrocarbon petroleum resin is particularly preferable.
Commercially available tackifying resins include: Imabu P-125, P-100, P-140 (above, manufactured by Idemitsu Kosan Co., Ltd.), Umex 1001 (manufactured by Sanyo Chemical Industries, Ltd.), Hiretsu T1115 (Mitsui Chemicals, Inc.) Co., Ltd.), Clearon K100 (manufactured by Yasuhara Chemical Co., Ltd.), ECR227, Escorez 2101 (manufactured by Tonex Co., Ltd.), Alcon P100 (manufactured by Arakawa Chemical Co., Ltd.), Regalrez 1078 (manufactured by Hercules (Hercules)) , Eastotac H-130R (Eastman Chemical Co., Ltd.), etc. (all are trade names).
The content of the tackifier resin in the glass adhesive of the present invention is based on the total amount of the glass adhesive of the present invention from the viewpoint of improving the tackiness, coating properties, and improving the wettability to the adherend due to a decrease in viscosity. , Preferably 20 to 60% by mass, more preferably 30 to 55% by mass. When the compounding amount of the tackifying resin in the glass adhesive of the present invention is 20% by mass or more, the tackiness is improved. When the blending amount of the tackifying resin in the glass adhesive of the present invention is 60% by mass or less, the adhesive strength of the glass adhesive does not decrease.

(wax)
The glass adhesive of the present invention may contain a wax.
Examples of the wax include animal wax, plant wax, carnauba wax, candelilla wax, wood wax, beeswax, mineral wax, petroleum wax, paraffin wax, microcrystalline wax, petrolatum, polyethylene wax, oxidized polyethylene wax, polypropylene wax, oxidized Examples thereof include polypropylene wax, higher fatty acid wax, higher fatty acid ester wax, and Fischer-Tropsch wax.
The content of the wax in the glass adhesive of the present invention is preferably 5 to 40% by mass with respect to the total amount of the glass adhesive, from the viewpoints of coatability and wettability improvement to the adherend due to viscosity reduction. More preferably, it is 10-30 mass%. When the wax content in the glass adhesive of the present invention is 40% by mass or less, the adhesive strength does not decrease.

(Additive)
Moreover, the adhesive agent for glass of this invention may contain various additives, such as a plasticizer, an inorganic filler, antioxidant, an initiator, as needed.
Examples of the plasticizer include waxes, phthalic acid esters, adipic acid esters, fatty acid esters, glycols, and epoxy polymer plasticizers.
Examples of the inorganic filler include clay, talc, calcium carbonate, barium carbonate and the like.
Examples of the antioxidant include trisnoniphenyl phosphite, distearyl pentaerythritol diphosphite, ADK STAB 1178 (manufactured by ADEKA), Stamilizer TNP (manufactured by Sumitomo Chemical Co., Ltd.), Irgaphos 168 (manufactured by BASF) , SandstabP-EPQ (manufactured by Sand), etc., 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-t-) Butyl-4'-hydroxyphenyl) propionate, Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd.), Irganox 1010 (manufactured by BASF), phenolic antioxidants, dilauryl-3,3'-thiodipropionate, penta Erythritol tetrakis (3-lauryl thiopropionate), Sumilizer TPL (Sumitomo Chemical) Gaku Co., Ltd.), Yoshinox DLTP (Yoshitomi Pharmaceutical Co., Ltd.), Antix L (manufactured by NOF Co., Ltd.) and other sulfur-based antioxidants.

The glass adhesive of the present invention is improved in various physical properties of the cured glass adhesive layer (optical properties such as mechanical strength, adhesiveness, transparency, heat resistance, light resistance, crosslinking speed, etc.) An acryloxy group-containing compound, a methacryloxy group-containing compound and / or an epoxy group-containing compound may be contained for adjustment, particularly improvement of mechanical strength.
Moreover, the adhesive agent for glass of this invention may contain the silane coupling agent as an adhesion | attachment improvement agent, in order to raise the adhesive force of a glass plate, a glass plate, or a plastic film further.

(Method for producing glass adhesive)
When the glass adhesive of the present invention contains a component other than the propylene homopolymer, the production method is not particularly limited, and the propylene homopolymer, ethylene polymer, and tackifying are performed as necessary. A resin, wax, or the like can be dry blended and mechanically mixed using a roll, a Banbury mixer, a kneader, a pressure kneader, a melting kettle equipped with a stirrer, or a uniaxial or biaxial extruder. At this time, it is also possible to heat as necessary. Moreover, after adding a compounding material to a suitable solvent and stirring this, after obtaining the uniform solution of a composition, the method of distilling a solvent off can also be used. Furthermore, if necessary, the composition can be molded as an adhesive by an extruder, an injection molding machine, a press machine or the like.

(Sealing agent for glass)
The glass adhesive of the present invention can be used, for example, as a glass sealing agent used when fitting into a door frame of an automobile and a window frame to be fitted, or a window frame of a vehicle, a building, or the like.
Further, in particular, when it is desired to improve the barrier function, it can be realized by forming a barrier layer on and around the side sealing agent layer and further forming a plier layer thereon.

(Glass molded products)
The glass adhesive of the present invention can be used when bonding glass molded products.
More specifically, the glass adhesive of the present invention can be suitably used as a glass adhesive for forming an interlayer film of laminated glass.
The laminated glass can be produced by bonding a glass plate and another glass plate or a plastic sheet using the glass adhesive of the present invention. The laminated glass thus obtained is It has an intermediate film made of an adhesive for glass.
The thickness of the interlayer film in the laminated glass is preferably about 10 μm to 50 mm, and more preferably 20 μm to 30 mm.

As a method for producing the laminated glass, for example, the glass adhesive of the present invention is preferably melted at 50 ° C to 300 ° C, more preferably at 100 ° C to 200 ° C, further preferably at 110 ° C to 180 ° C. The method of apply | coating to a glass plate and bonding can be mentioned.
The method of applying the glass adhesive is not particularly limited. For example, roll coating, wide slit die, knife coating, dot coating, multi-line coating, rotary heat coating, swirling method, or a melt blow method or air assisted in a large area. The spray application by the spray method is mentioned. The coated glass plate is subsequently bonded to another glass plate or plastic sheet within the so-called open time.

  As another embodiment of the method for producing laminated glass, it is also possible to mold an adhesive for glass, laminate a plastic film, degas this sandwich structure, and then press it under heating. Then, if desired, a laminated glass can be obtained by carrying out a hard coat process on a plastic film. Or after the said lamination | stacking process, a hard-coat can be apply | coated, and after UV hardening, it can press under heating and can also obtain a laminated glass.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Synthesis example 1
[Complex A ((1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride)]
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) was synthesized according to the description in Reference Example 1 of Japanese Patent No. 4053993.

Example 1
(Production of propylene homopolymer)
To a stainless steel reactor with a stirrer and an internal volume of 68 m ³ , n-heptane 5.2 m ³ / h, triisobutylaluminum 0.6 mol / h, dimethylanilinium tetrakispentafluorophenylborate, complex A and The catalyst component obtained by previously contacting triisobutylaluminum and propylene was continuously fed at 0.7 mmol / h per zirconium.
Propylene and hydrogen were continuously supplied at a polymerization temperature of 85 ° C. so that the gas phase hydrogen concentration was 5.0 mol% and the total pressure in the reactor was maintained at 1.7 MPa · G.
To the resulting polymerization solution, Irganox 1010 (trade name, manufactured by BASF) was added so that the content in the polymerization solution was 1000 ppm, and the solvent was removed to obtain a propylene homopolymer.

About the propylene homopolymer obtained as mentioned above, mesopentad fraction [mmmm], weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) and melting point (Tm-D) were measured by the following evaluation methods. .
[Evaluation of stereoregularity: NMR measurement]
The ¹³ C-NMR spectrum was measured with the following apparatus and conditions. In addition, the attribution of the peak followed the method proposed by A. Zambelli et al. In “Macromolecules, 8, 687 (1975)”. The results are shown in Table 1.
Device: JEOL Ltd., JNM-EX400 type ¹³ C-NMR device Method: Proton complete decoupling method Concentration: 220 mg / ml
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

<Calculation formula>
M = m / S × 100
R = γ / S × 100
S = Pββ + Pαβ + Pαγ
S: Signal intensity of side chain methyl carbon atoms of all propylene units Pββ: 19.8 to 22.5 ppm
Pαβ: 18.0 to 17.5 ppm
Pαγ: 17.5 to 17.1 ppm
γ: Racemic pentad chain: 20.7 to 20.3 ppm
m: Mesopentad chain: 21.7-22.5 ppm

The mesopentad fraction [mmmm] was determined according to the method proposed by A. Zambelli et al. In “Macromolecules, 6, 925 (1973)”, and the methyl of the ¹³ C-NMR spectrum was obtained. The meso fraction and the racemic meso-racemic meso fraction in pentad units in the polypropylene molecular chain measured by the group signal.

[Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) measurement]
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC). For the measurement, the following apparatus and conditions were used, and a weight average molecular weight in terms of polystyrene was obtained. The results are shown in Table 1.
<GPC measurement device>
Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
<Measurement conditions>
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml
Injection volume: 160 μl
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

[Melting point (Tm-D)]
Using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer Co.), a melting endotherm obtained by holding 10 mg of a sample at −10 ° C. for 5 minutes in a nitrogen atmosphere and then raising the temperature at 10 ° C./min. The melting point (Tm-D) was determined from the peak top of the peak observed on the highest temperature side of the curve. The results are shown in Table 1.

(Preparation of test piece)
The propylene homopolymer obtained above is molded using a press molding machine at a heater set temperature of 160 ° C. to produce a resin plate of 150 × 150 mm and a thickness of 1 mm, from which 60 × 60 mm is cut out, and a test piece It was.

(Evaluation of specimen)
The test piece obtained as described above was evaluated for YI (transmission), haze, total light transmittance, and gloss by the following evaluation methods. The evaluation results are shown in Table 2.
YI (transmission): Measured according to JIS Z8722.
Haze, total light transmittance: measured in accordance with JIS K7136.
Gloss: Measured according to JIS Z8741.

(Production of film)
The propylene homopolymer obtained above was formed into a film having a thickness of 100 μm at a set temperature of 150 ° C. using a hot roll bar coater manufactured by MEC.

(Production of laminated glass)
A hot plate (HPD-3000, manufactured by ASONE Co., Ltd.) was set at 170 ° C., and an aluminum foil (Mitsubishi Aluminum Nipper Foil thickness 12 μm) was allowed to stand on the hot plate.
Next, the film was cut into the same shape on a glass degreased with acetone (slide glass, manufactured by Toshin Riko Co., Ltd., 26 × 76 mm), and in this state, both were placed on a hot plate at the same time. Heated for minutes. In addition, the surface temperature of the glass upper surface was 140 degreeC.
Next, another defatted slide glass was placed on the melted film, and a 2 kg weight was placed thereon and held for 1 minute. Thereafter, the weight was removed first, and then the laminated glass bonded together was moved onto a flat plate, and further, a 2 kg weight was placed on the plate again and left for 2 minutes to cool. Then, it was left for one day in an environment of 23 ° C. and 50% RH to obtain a laminated glass of the present invention.

(Peel test)
When the peeling test was carried out by holding the end face of the obtained laminated glass, peeling was impossible and the adhesive strength was good.

Comparative Example 1
For the amorphous polyalphaolefin (Vestplast 750, manufactured by Evonik Degussa), the weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), and melting point (Tm-D) were measured in the same manner as in Example 1. The results are shown in Table 1.
Moreover, in Example 1, it replaced with the propylene homopolymer obtained in Example 1, and produced the test piece like Example 1 except having used the said amorphous polyalphaolefin, YI ( Transmission), haze, total light transmittance, and gloss were evaluated. The evaluation results are shown in Table 2.
Further, in Example 1, instead of the propylene homopolymer obtained in Production Example 1, amorphous polyalphaolefin (Vestplast 750, manufactured by Evonik Degussa) was used in the same manner as in Example 1. When a laminated glass was produced and a peel test was performed, it was not peelable and the adhesive strength was good.

  From Table 2, the adhesive for glass of the present invention obtained in Example 1 has a low YI and is therefore less colored, has a low haze and a high total light transmittance, is excellent in transparency, and has a high gloss. It was confirmed that the film was smooth and poor in appearance at the interface with glass, and showed good adhesiveness as an adhesive for glass.

  The glass adhesive of the present invention is useful when producing laminated glass used as a windshield or door glass for automobiles.

Claims (4)

A glass adhesive comprising a propylene homopolymer satisfying the following (1) to (3):
(1) Mesopentad fraction [mmmm] is 20 to 80%.
(2) The weight average molecular weight (Mw) is 10,000 to 500,000.
(3) Molecular weight distribution (Mw / Mn) is 2.5 or less.   A glass sealing agent comprising the glass adhesive according to claim 1.   The glass molded product bonded together using the adhesive agent for glass of Claim 1.   A laminated glass comprising a glass plate and a glass plate or a plastic sheet sandwiching an intermediate film, wherein the intermediate film comprises the glass adhesive according to claim 1.