TWI487732B - Photocurable polysiloxane urethane (meth)acrylate composition, adhesive and curing product - Google Patents

Description

Photocurable siloxane polyamine ester (meth) acrylate composition, Adhesive and hardened

The present invention relates to a photocurable adhesive composition, and more particularly to a photocurable methoxyalkane (meth)acrylic acid comprising the photocurable methoxyalkane (meth) acrylate and thiol compound. Ester composition.

At present, in the display device, a transparent cover lens made of a material such as glass, acrylic resin plate, polycarbonate plate or the like and a touch panel or a touch panel and a display element are pasted. Agent. The following agents are generally classified into a thermosetting type and a photocuring type, and the photocuring type adhesive requires less hardening time than the thermosetting type adhesive, and is suitable for use in a production line.

U.S. Patent No. 6,265,476 discloses a radiation-curable composition. In the specific examples of the specification, the radiation hardening composition comprises urethane acrylate oligomer, N-vinylfo rmamide, γ-mercaptopropyltrimethyl Γ-mercaptopropyltrimet hoxysilane and photoinitiator (IRGACURE I184). Revealed in this patent case The radiation hardening composition shown forms a hardened material in the subsequent step, so that the cured product has a tensile fracture length of 1200%. Although the radiation hardening composition can form a cured product having a tensile fracture length of 1200%, the radiation hardening composition has a problem that the volume shrinkage rate is too high, so that the hardened material formed by the heat hardened material is easily subjected to thermal shock. There is a problem with peeling.

In view of the above, improving the composition to provide a suitable tensile fracture length and volume shrinkage ratio for the cured product is a subject that can be further broken by those skilled in the art.

Accordingly, a first object of the present invention is to provide a photocurable siloxane polyamine (meth) acrylate composition. The photocurable siloxane polyamine ester (meth) acrylate composition is applied to the cured product in a subsequent manner, so that the tensile breaking length of the cured product is more than 680%, and the volume shrinkage ratio is 1.95% or less.

Thus, the photocurable oxirane polyamine ester (meth) acrylate composition of the present invention comprises: a methoxy olefin polyamine ester (meth) acrylate comprising a polymerization product obtained by polymerization of a reactant, the reaction The present invention has a dihydroxy-containing polyoxyalkylene-based polymer, a diisocyanate-based compound, and a hydroxyl group-containing (meth) acrylate-based compound, wherein the weight average molecular weight range of the dihydroxy-containing polyoxyalkylene-based polymer It is 5,000 or less, and the molar ratio of the amount of the diisocyanate-based compound to the amount of the dihydroxy-containing polyoxyalkylene-based polymer is from 1.05 to 1.45.

a compound containing an ethylenically unsaturated group; a photoinitiator; and a thiol compound.

A second object of the invention is to provide an adhesive.

Thus, the adhesive of the present invention comprises the above photocurable siloxane polyamine ester (meth) acrylate composition.

A third object of the present invention is to provide a cured product having a tensile fracture length of more than 680% and a volume shrinkage ratio of 1.95% or less.

Thus, the cured product of the present invention is formed of the above-mentioned adhesive.

The effect of the present invention is to make the photohardenable enamel of the present invention by using a thiol compound and controlling the amount of the diisocyanate compound to be used in an amount of from 1.05 to 1.45. The oxyalkylene polyamine (meth) acrylate composition is applied to the cured product in the subsequent application, so that the cured product has a tensile fracture length of more than 680% and a volume shrinkage ratio of 1.95% or less.

In the present invention, the photocurable oxirane polyamine ester of the present invention is obtained by using a thiol compound and controlling the amount of the diisocyanate compound to be used in an amount of from 1.05 to 1.45 in terms of the amount of the dihydroxy-containing polyoxyalkylene-based polymer. The subsequent application of the methyl acrylate composition to the cured product allows the cured product to have a tensile fracture length of greater than 680% and a volumetric shrinkage of 1.95% or less. In addition to the above, the photocurable oxirane polyamine ester of the present invention (methyl The oxirane polyamine ester (meth) acrylate in the acrylate composition contains a siloxane chain segment, and the cured product formed of the photocurable siloxane polyamine ester (meth) acrylate composition has It has the advantages of good penetration and strong light resistance and is not easy to yellow.

Herein, the (meth)acrylate [(meth)acrylate] means acrylate and/or methacrylate.

The photocurable polysiloxane urethane (meth)acrylate composition of the present invention comprises: the polysiloxane urethane (meth)acrylate comprises a polymerization product obtained by polymerization of a reactant having a dihydroxy-containing polysiloxane diol, a diisocyanate compound, and a hydroxyl group-containing (meth) acrylate compound Wherein the dihydroxy-containing polyoxyalkylene-based polymer has a weight average molecular weight in the range of 5,000 or less, and the molar ratio of the amount of the diisocyanate-based compound to the dihydroxy-containing polyoxyalkylene-based polymer is 1.05 to 1.45; a compound containing an ethylenically unsaturated functional group; a photoinitiator; and a thiol compound.

Preferably, the amount of the diisocyanate compound and the amount of the dihydroxy-containing polyoxyalkylene-based polymer are from 1.25 to 1.45.

Further description of each component in the photocurable siloxane polyamine ester (meth) acrylate composition of the present invention will be further described below:

<<Oxyalkylene polyamine ester (meth) acrylate>>

The oxirane polyamine ester (meth) acrylate comprises a polymerization product obtained by polymerization of a reactant having a dihydroxy-containing polysiloxane diol and a diisocyanate compound. And a hydroxyl group-containing (meth) acrylate compound. The polymerization process may optionally be carried out by adding a catalyst, a stabilizer or a diluent.

The oxirane polyamine ester (meth) acrylate is prepared by mixing the diisocyanate compound, the dihydroxy-containing polyoxyalkylene polymer, a diluent, and a catalyst, and then adding a stabilizer. The polyoxyalkylene (meth) acrylate can be obtained by carrying out a polymerization reaction with a hydroxyl group-containing (meth) acrylate compound. Preferably, the polymerization has an operating temperature in the range of from 40 °C to 65 °C. Preferably, the polymerization has an operating time ranging from 4.5 hours to 5.58 hours.

Preferably, the oxirane polyamine ester (meth) acrylate has a weight average molecular weight ranging from 20,000 to 36,000.

Preferably, the oxirane polyurethane (meth) acrylate has a viscosity in the range of 19,000 to 26,000 mpas at 25 °C.

[Dihydroxy-containing polyoxyalkylene-based polymer]

Preferably, the dihydroxy-containing polyoxyalkylene-based polymer is represented by the formula (I):

Wherein R ¹ and R ² are each a C ₁ to C ₆ alkylene group; z is an integer of 1 to 120; m and n are each an integer of 1 to 5; and x and y are each an integer of 0 or 1 to 3.

Preferably, the dihydroxy-containing polyoxyalkylene-based polymer has a weight average molecular weight ranging from 300 to 2,000.

Commercially available products of the dihydroxy-containing polyoxyalkylene-based polymer are, for example but not limited to, Q4-3667 manufactured by Dow Corning; X-22-160AS, KF-6001, KF-6002 manufactured by Shin-Etsu, or KF-6003. In the specific example of the photocurable oxirane polyamine (meth) acrylate composition of the present invention, the dihydroxy-containing polyoxyalkylene-based polymer to be used is X-22-160AS and KF-6001.

[Diisocyanate compound]

The diisocyanate compound is selected from an aliphatic diisocyanate compound, an aromatic diisocyanate compound, or a combination thereof.

The aliphatic diisocyanate compound may be used singly or in combination, and the aliphatic diisocyanate compound is, for example but not limited to, hexamethyl diisocyanate (hexane-1, 6-diisocyanate, HDI for short), 2, 2, 4 -2,2,4-trimethylhexane-1,6-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate (2,4,4-trimethylhexane- 1,6-diisocyanate), 1,4-diisocyanate, 1,12-didecane diisocyanate, 4,4'- Dicyclohexylmethane diisocyanate (4,4'-dicyclohexylmethane diisocyanate), isophorone diisocyanate (isoph Orone diisocyanate (IPDI for short), 1,4-cyclohexane-1,4-diisocyanate, cyclohexane-1,2-diisocyanate, or hydrogenated benzodiazepine Hydrogenated xylylene diisocyanate and the like.

The aromatic diisocyanate compound may be used singly or in combination, and the aromatic diisocyanate compound is, for example but not limited to, any isomer of toluene diisocyanate (TDI) and a mixture thereof, 1,5-naphthalene. 2,4'-diphenylmethane diisocyanate ), xylylene diisocyanate (XDI), 2,2-diphenylpropane-4,4'-diisocyanate, p-phenylene Isocyanate (p-phenylene diisocyanate), m-phenylene diisocyanate, diphenyl-4,4'-diisocyanate, diphenyl hydrazine-4,4'- Diphenylsulphone-4, 4'-diisocyanate, or 1-chlorobenzene-2,4-diisocyanate, and the like.

In a specific example of the photocurable siloxane polyamine (meth) acrylate composition of the present invention, the diisocyanate used is isophorone diisocyanate.

[Hydroxy group-containing (meth) acrylate compound]

The hydroxyl group-containing (meth) acrylate compound is used as a terminal blocking agent in the reaction for synthesizing the oxirane polyamine ester (meth) acrylate. The inclusion The hydroxy (meth) acrylate type compound may be used singly or in combination, and the hydroxyl group-containing (meth) acrylate type compound is, for example but not limited to: (meth)acrylic acid-β-hydroxyethyl [β-hydroxyethyl ( Meth)acrylate, β-hydroxypropyl(meth)acrylate, β-hydroxybutyl(meth)acrylate, and diethyl 2 Alcohol mono(meth)acrylate [di(propylene glycol) mono(meth)acrylate], dipropylene glycol mono(meth)acrylate [di(propylene glycol) mono(meth)acrylate], 1,3-propanediol mono ( 1,3-propylene glycol mono (meth)acrylate, or 1,4-butanediol (meth)acrylate, and the like. In a specific example of the photocurable siloxane polyamine (meth) acrylate composition of the present invention, the hydroxyl group-containing (meth) acrylate compound used is β-hydroxyethyl methacrylate. Preferably, the hydroxyl group-containing (meth) acrylate-based compound is used in an amount of from 0.1 to 1 in terms of the amount of the dihydroxy-containing polyoxyalkylene-based polymer. More preferably, the amount of the hydroxyl group-containing (meth) acrylate-based compound and the dihydroxy-containing polyoxyalkylene-based polymer are from 0.2 to 0.5.

[catalyst]

The catalyst can promote the reaction of the hydroxyl group of the dihydroxy-containing polyoxyalkylene-based polymer with the diisocyanate compound. The catalyst may be used singly or in combination, and the catalyst is, for example but not limited to, dibutyltin dilaurate (DBTDL), dibutyltin dichloride, stannous octoate, Sanya. Triethylenediamine, or N,N,N',N",N"-pentamethyldi Ethylene triamine (N, N, N', N", N"-pentamethyldiethylenetriamine) and the like. In a specific example of the photocurable siloxane polyamine (meth) acrylate composition of the present invention, the catalyst used is dibutyltin dilaurate. Preferably, the catalyst is used in an amount ranging from 0.01 to 10 parts by weight based on 100 parts by weight of the total of the dihydroxy-containing polyoxyalkylene-based polymer. More preferably, the catalyst is used in an amount ranging from 0.12 to 0.14 parts by weight based on 100 parts by weight of the total of the dihydroxy-containing polyoxyalkylene-based polymer.

[Stabilizer]

The stabilizer is not particularly limited, and the purpose is to prevent the (meth) acrylate in the hydroxyl group-containing (meth) acrylate compound from being polymerized in the process of preparing the oxirane polyamine ester (meth) acrylate. The stabilizer may be used singly or in combination, and the stabilizer may be, for example but not limited to, 4-methoxyphenol (MEHQ), 2,6-di(t-butyl)-4-cresol ( 2,6-di-tert-butyl-4-methylphenol), or 2,2'-methylene-bis(4-methyl-6-tert-butylphenol) [2,2'-methylene bis (6 -tert-butyl-m-cresol)]. In a specific example of the photocurable siloxane polyamine ester (meth) acrylate composition of the present invention, the stabilizer used is 4-hydroxyanisole. Preferably, the stabilizer is used in an amount ranging from 0.001 to 1 part by weight based on 100 parts by weight of the total of the dihydroxy-containing polyoxyalkylene-based polymer. More preferably, the stabilizer is used in an amount ranging from 0.06 to 0.08 parts by weight based on 100 parts by weight of the total of the dihydroxy-containing polyoxyalkylene-based polymer.

[diluent]

The diluent is not particularly limited, and the purpose is to adjust the viscosity in the process of preparing the oxirane polyamine (meth) acrylate to avoid viscosity. High causes inconvenience in operation, and at the same time, it can participate in polymerization when it is applied to the hardened material. The diluent may be used singly or in combination, and the diluent is, for example but not limited to, (dodecyl (meth)acrylate], 2-ethylhexyl (meth)acrylate (2-ethylhexyl (meth) Meth)acrylate], isodecyl(meth)acrylate, 2-propylheptyl(meth)acrylate, 2-phenoxyethyl (2-phenoxyethyl (meth)acrylate], ethoxyethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth) Acrylate], isobornyl (meth)acrylate, tridecyl(meth)acrylate, or ethoxylated phenol (meth)acrylate [ Ethoxylated phenol (meth)acrylate]. In a specific example of the photocurable siloxane polyamine ester (meth) acrylate composition of the present invention, the diluent used is lauryl acrylate. Preferably, the diluent is used in an amount ranging from 5 to 1000 parts by weight based on 100 parts by weight of the total of the dihydroxy-containing polyoxyalkylene-based polymer. More preferably, the diluent is used in an amount ranging from 33 to 40 parts by weight based on 100 parts by weight of the total of the dihydroxy-containing polyoxyalkylene-based polymer.

<<Compounds containing ethylenically unsaturated groups>>

The ethylenically unsaturated group-containing compound can lower the viscosity of the oxirane polyamine (meth) acrylate composition to a suitable range, and at the same time, can be involved in polymerization when it is applied to a cured product.

The ethylenically unsaturated group-containing compound may be used singly or in combination, and the ethylenically unsaturated group-containing compound is, for example but not limited to, a (meth) acrylate-based compound. The (meth) acrylate-based compound such as, but not limited to, a C ₁ to C ₂₀ chain hydrocarbyl (meth) acrylate, a C ₁ to C ₂₀ alicyclic hydrocarbon (meth) acrylate, or other (A) Base) acrylate.

The C ₁ to C ₂₀ chain hydrocarbon (meth) acrylate such as, but not limited to, methyl (meth) acrylate, ethyl (meth) acrylate , propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, Isobutyl(meth)acrylate, t-butyl(meth)acrylate,2-ethylhexyl (2-ethylhexyl) (meth)acrylate], heptyl (meth)acrylate, octyl(meth)acrylate,isooctyl(meth)acrylate ], (nonyl (meth)acrylate], decyl (meth)acrylate, isodecyl (meth)acrylate, (a) Base, dodecyl (meth)acrylate, tridecyl (meth)acrylate, undecyl (meth)acrylate, Or lauryl (meth)acrylate [dodecyl (meth) acryl Ate] and so on.

The C ₁ to C ₂₀ alicyclic hydrocarbon (meth) acrylate such as, but not limited to, cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate [ 4-butylcyclohexyl(meth)acrylate], isobornyl(meth)acrylate,bornyl(meth)acrylate,bicyclodecyl (meth)acrylate [tricyclodecanyl (meth)acrylate], dicyclopentanyl (meth)acrylate, or dicyclopentenyl (meth)acrylate.

The other (meth) acrylates are, for example but not limited to, benzyl (meth)acrylate, 2-phenoxyethyl (meth) acrylate, (meth) acrylate ethoxylate Ethyl ethoxyethyl ester, (meth)acrylic acid tetrahydrofuran methyl ester, or ethoxylated phenol (meth) acrylate or the like.

In the specific example of the photocurable siloxane polyamine (meth) acrylate composition of the present invention, the ethylenically unsaturated group-containing compound used is lauryl acrylate.

Preferably, the ethylenically unsaturated group-containing compound is used in an amount ranging from 0.1 to 100 parts by weight based on 100 parts by weight of the total of the oxyalkylene polyamine (meth) acrylate. More preferably, the ethylenically unsaturated group-containing compound is used in an amount ranging from 17 to 24 parts by weight based on 100 parts by weight of the total of the oxirane polyurethane acrylate.

<<thiol compound>>

The thiol compound needs to have good compatibility with the oxirane polyamine ester (meth) acrylate to avoid phase separation of the photocurable siloxane polyamine ester (meth) acrylate composition of the present invention. The thiol compound may be used singly or in combination, and the thiol compound is, for example but not limited to, tridecyl 3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate) [trimethylolpropane tris (3-mercaptopropionate), abbreviated as TMMP], 1,4-bis(3-mercaptobutyryloxy)butane [1,4-bis(3-mercaptobutyryloxy)butane], pentaerythritol tetrakis(3-mercaptobutyric acid) Ester) [pentaerythritol tetrakis (3-mercaptobutylate)], pentaerythritol tetrakis (3-mercaptopropionate), 3-methoxybutyl- 3-methoxybutyl- 3-mercaptopropionate), or octyl 3-meracaptopropionate, and the like. In a specific example of the photocurable siloxane polyamine (meth) acrylate composition of the present invention, the thiol compound used is trimethylolpropane tris(3-mercaptopropionate). Preferably, the thiol compound is used in an amount ranging from 0.1 to 10 parts by weight based on 100 parts by weight of the total of the oxyalkylene polyamine (meth) acrylate. More preferably, the thiol compound is used in an amount ranging from 0.4 to 1 part by weight based on 100 parts by weight of the total of the oxyalkylene polyamine (meth) acrylate.

<<Light starter>>

The photoinitiator can be used singly or in combination, and the photoinitiator is, for example but not limited to:

(1) phosphine oxide: arylphosphine oxide, acylphosphine oxide, bisacylphosphine oxide, 2,4,6- 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), bis(2,6-dimethoxybenzylidene)-2,4,4-tri Bis(2,6-dimethoxybenzoyl-2,4,4-trimethylpentyl phosphine oxide), bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide Bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide, referred to as I-819], 2,6-diethylbenzoyldiphenylphosphine o (2,6-diethylbenzoyldiphenylphosphine o Xide), 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzhydryldiphenylphosphine oxide (2,6) -dichlorobenzoyldiphenylphosphine oxide 0,2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, or 2,4,6-trimethylbenzene 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, etc.;

(2) Carbonyl compounds: acetophenone, benzophenone, biphenylketone, 1-hydroxy-1-benzhydrylcyclohexane (1-hydroxy-) 1-benzoylcyclohexane, referred to as I-184), 2-hydroxy-2-methyl-1-phenyl-propyl-1-one (2-hydroxy-2-methyl-1-phenyl-propan-1-one, abbreviated Darocur1173), or 2,2-dimethoxy-2-phenylacetophenone (I-651).

(3) Triazine compound: 2-[2-(4-methoxy-phenyl)-vinyl]-4,6-bis-trichloromethyl-[1,3,5] {2-[2-(4-methoxy-phenyl)-vinyl]-4,6-bis-trichloromethyl-[1,3,5]triazine}, 2-(4-methoxy-naphthalen-1-yl) -4,6-bis-trichloromethyl-[1,3,5]triazine {2-(4-methoxy-naphthalen-1-yl)-4,6-bis-trichloromethyl-[1,3, 5]triazine}, 2-benzo[1,3]dioxapenta-5-yl-4,6-bis-trichloromethyl-[1,3,5]triazine {2-benzo[1, 3] dioxol-5-yl-4,6-bis-trichloromethyl-[1,3,5]triazine}, 2-methyl-4,6-bis(trichloromethyl)-s-triazine [2- Methyl-4,6-bis(trichloromethyl)-s-triazine], 2-phenyl-4,6-bis(trichloromethyl)-s-triazine [2-phenyl-4,6-bis(trichloromethyl) -s-triazine, or 2- Naphthyl-4,6-bis(trichloromethyl)-s-triazine [2-naphthyl-4,6-bis(trichloromethyl)-s-triazine];

(4) Aminocarbonyl compounds and oxime compounds: 1-benzyl-1-dimethylamino-1-(4-morpholinyl-benzylidene)propane [1] -benzyl-1-dimethylamino-1-(4-morpholino-benzoyl)propane, referred to as I-369], 2-morpholinyl-2-(4-methylindenyl) benzhydrylpropane [2-morpholyl-2- (4-methylmercapto) benzoylpropane, referred to as I-907], ethylanthraquinone, 4-benzoyl-4-methyldiphenylsulfide, benzoin ( Benzoinbutylether), 2-hydroxy-2-benzoylpropane, 2-hydroxy-2-(4-isopropyl)benzimidylpropane [2-hydroxy-2-(2-hydroxy-2-) 4-isopropyl)benzoylpropane], 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzhydrazide ( Benzyl methylformate), 1,7-bis(9-acridinyl)heptane, 9-n-butyl-3,6-bis(2-morpholinyl- Isobutyryl) 9-n-butyl-3,6-bis(2-morpholino-isobutyloyl)carbazole, or 10-butyl-2-chloroacridone (10-butyl) -2-chloroacrydone) and so on.

In a specific example of the photocurable oxirane polyamine (meth) acrylate composition of the present invention, the photoinitiator used is bis(2,4,6-trimethylbenzylidene)phenylphosphine. Oxide. Preferably, the photoinitiator is used in an amount ranging from 0.01 to 10 parts by weight based on 100 parts by weight of the total of the oxyalkylene polyamine (meth) acrylate. More preferably, the alumoxane polyurethane (A The total amount of the acrylate is 100 parts by weight, and the photoinitiator is used in an amount ranging from 0.1 to 0.5 parts by weight.

The method for producing the photocurable siloxane polyamine ester (meth) acrylate composition of the present invention is not particularly limited, and for example, the oxirane polyamine ester (meth) acrylate, the ethylenically unsaturated group-containing compound, The photoinitiator and the thiol compound are placed in a stirrer and stirred uniformly, or may be further subjected to defoaming after mixing.

The adhesive of the present invention comprises the above photocurable siloxane polyamine ester (meth) acrylate composition.

The adhesive of the present invention can be applied to a substrate, a panel or a component made of a material such as glass, acrylic resin, polycarbonate, etc., and is particularly suitable for application to glass to glass.

The cured product of the present invention is formed of the above-mentioned adhesive. This formation method can harden the adhesive by irradiating ultraviolet light or visible light.

The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.

<Example> [Synthesis Example 1] Synthesis of a polyoxyalkyl ester (meth) acrylate (A1)

11.11 g (0.05 mol) of IPDI, 40 g (0.04 mol) of X-22-160AS, 9.2 g of lauryl acrylate and 0.05 g of DBTDL were placed in a 600 ml round bottom flask under nitrogen atmosphere at 40 The reaction was continuously stirred at ° C for 1.5 hours, followed by the addition of 0.03 g of MEHQ and 1.17 g (0.010). 1 mol) of β-hydroxyethyl methacrylate, and reacted at 65 ° C for 4 hours to obtain a polyoxyalkylene methacrylate having a viscosity of 25441 mpas and a weight average molecular weight of 20001.

[Synthesis Examples 2 to 3]

The oxirane polyamine ester (meth) acrylate of Synthesis Example 2 and Synthesis Example 3 was obtained in the same manner as in Preparation Synthesis Example 1, and the kinds and amounts of the respective components are shown in Table 1.

[Example 1] Preparation of photocurable siloxane polyamine ester (meth) acrylate composition

81 g of the oxirane polyamine ester methacrylate of Synthesis Example 1, 17.9 g of lauryl acrylate, 0.4 g of I819 and 0.7 g of TMMP were stirred and homogenized at 25 ° C, followed by a centrifugal defoamer. After defoaming, a photocurable siloxane polyamine ester (meth) acrylate composition can be obtained. And each property test, the test results are shown in Table 2.

[Comparative Examples 1 to 2]

The oxirane polyamine ester (meth) acrylate compositions of Comparative Examples 1 to 2 were obtained in the same manner as in Production Example 1, wherein the kinds and amounts of the respective components are shown in Table 2. And each property test, the test results are shown in Table 2.

[Property test]

Penetration and yellow index (YI value): In order to facilitate the description of the measurement process, the following is described in the first embodiment, and the remaining examples and comparative examples are measured in accordance with the method.

Two sheets of alkali-free glass having a thickness of 0.63 mm were taken, and a circular coating zone having a diameter of 40 mm was enclosed on one of the alkali-free glasses, and the photocurable oxirane polyurethane (meth) acrylate of Example 1 was used. The composition fills the circular coating zone and has a coating thickness of 300 μm, and then another piece of alkali-free glass is overlaid on the alkali-free glass, after which an exposure machine is used (manufacturer: FUSION UV SYSTEMS, model: F300S) +AJ-6-UVL) Exposure was carried out under the conditions of an illuminance of 2000 mW/cm ² and a total exposure energy of 5000 mJ/cm ² to form a test piece to be tested. The transmittance and yellowness index of the test piece were measured by an ultraviolet light visible spectrometer, and the wavelength range used was 350 nm to 800 nm.

Haze: The haze of the test piece in the property test 1 was measured by a Nippon Denshaku NDH 5000 machine, and the haze was calculated as follows: haze = diffusion pass rate (Dfs) ÷ full permeability (Tt) × 100%.

Tensile strength, Elongation at break, and Modulus: The oxirane polyamine ester (meth) acrylate compositions of Examples 1 to 2 and Comparative Examples 1 to 2 The test piece was prepared in accordance with the standard test method of ASTM D638-03 Type V, respectively. Each piece to be tested had a thickness of 3.2 mm and was tested at room temperature using a universal tensile machine (manufacturer: SHIMAZU, model: EZ-L, tensile speed: 10 mm/min.).

Glass-to-glass adhesion strength (Tensile Adhesion, unit kPa): To facilitate the description of the measurement process, the following is described in the first embodiment, and the remaining examples and comparative examples are measured in accordance with this method.

Two pieces of 76 mm × 26 mm and 1 mm thick alkali-free glass were taken, and a circular coating area of 5 mm in diameter was drawn on one of the alkali-free glass. Next, the oxirane polyurethane of Example 1 was taken. The (meth) acrylate composition is coated on the circular coating zone, after which another piece of alkali-free glass is coated on the alkali-free glass and pressurized to a gap of 300 μm between the two alkali-free glasses. . Next, exposure was carried out using an exposure machine under the conditions of an illuminance of 2000 mW/cm ² and a total exposure energy of 5000 mJ/cm ² to form a test piece to be tested. The adhesion strength of the test piece is measured by a universal tensile machine, and the measurement method is as follows: the alkali-free glass in the test piece is peeled off at a speed of 2 mm/min and parallel to the alkali-free glass, and measured. The stress at the time when the alkali-free glass was peeled off was calculated by the following formula: adhesion strength (kPa) = stress when the alkali-free glass was peeled off, and the area of the round coating region.

Volume shrinkage ratio (%): The liquid specific gravity of the oxirane polyamine ester (meth) acrylate composition of Examples 1 to 2 and Comparative Examples 1 to 2 and the solid specific gravity after photohardening were measured in accordance with JIS-K-6833, and then by liquid The volumetric shrinkage ratio is calculated from the volume ratio of the solid.

a: The amount used is 100 parts by weight based on the total amount of the dihydroxy-containing polyoxyalkylene-based polymer; "--" means that it is not added.

b: The amount is calculated based on 100 parts by weight of the total amount of the oxyalkylene polyamine ester (meth) acrylate; "--": indicates that it is not added.

The results of the experimental data of Table 2 show that the cured product formed from the photocurable siloxane polyamine ester (meth) acrylate composition of Example 1 and Example 2 has a tensile fracture length of more than 680%, and the volume The shrinkage rate is 1.95% or less.

As is clear from Comparative Example 1, the composition did not use a thiol compound, so that the tensile fracture length (306.6%) and the volume shrinkage ratio (1.98%) of the cured product formed therefrom were not good.

It can be seen from Comparative Example 2 that although the composition uses a thiol compound However, the amount of the diisocyanate compound in the polyoxyalkylene (meth) acrylate and the amount of the dihydroxy-containing polyoxyalkylene-based polymer are 1.5, so that the hardened material formed therefrom The tensile fracture length (204.2%) and the volume shrinkage ratio (2.02%) were not good.

In summary, the photocurable oxirane polyamine ester (meth) acrylate composition of the present invention uses a thiol compound, and controls the amount of the diisocyanate compound and the amount of the dihydroxy-containing polyoxyalkylene polymer. The Mohr ratio is 1.05 to 1.45, so that the photocurable oxyalkylene polyamine ester (meth) acrylate composition of the present invention can be applied to the hardened material in the subsequent application, so that the tensile fracture length of the cured product is greater than 680%, so The object of the invention is achieved.

The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.

Claims (10)

A photocurable siloxane polyamine ester (meth) acrylate composition comprising: a methoxy olefin polyamine ester (meth) acrylate comprising a polymerization product obtained by polymerization of a reactant, the reactant having a dihydroxy polyoxyalkylene-based polymer, a diisocyanate-based compound, and a hydroxyl group-containing (meth) acrylate-based compound, wherein the dihydroxy-containing polyoxyalkylene-based polymer has a weight average molecular weight range of 5,000 or less And the molar ratio of the diisocyanate-based compound to the dihydroxy-containing polyoxyalkylene-based polymer is from 1.05 to 1.45; the ethylenically unsaturated group-containing compound; the photoinitiator; and the thiol compound. The photocurable siloxane polyamine ester (meth) acrylate composition according to claim 1, wherein the total amount of the oxyalkylene polyamine (meth) acrylate is 100 parts by weight, the thiol compound The amount used is in the range of 0.1 to 10 parts by weight. The photocurable siloxane polyamine ester (meth) acrylate composition according to claim 1, wherein the oxirane polyamine ester (meth) acrylate has a weight average molecular weight ranging from 20,000 to 36,000. The photocurable siloxane polyamine ester (meth) acrylate composition according to claim 1, wherein the dihydroxy-containing polyoxyalkylene-based polymer is represented by the formula (I): Wherein R ¹ and R ² are each a C ₁ to C ₆ alkylene group; z is an integer of 1 to 120; m and n are each an integer of 1 to 5; and x and y are each an integer of 0 or 1 to 3. The photocurable siloxane polyamine ester (meth) acrylate composition according to claim 1, wherein the dihydroxy-containing polyoxyalkylene-based polymer has a weight average molecular weight ranging from 300 to 2,000. The photocurable oxirane polyamine (meth) acrylate composition according to claim 1, wherein the total amount of the oxirane polyamine (meth) acrylate is 100 parts by weight, and the ethylenicity is not The saturated group compound is used in an amount ranging from 0.1 to 100 parts by weight. The photocurable oxirane polyamine (meth) acrylate composition according to claim 1, wherein the photoinitiator is 100 parts by weight based on the total amount of the oxirane polyamine (meth) acrylate. The amount used is in the range of 0.01 to 10 parts by weight. The photocurable oxirane polyamine (meth) acrylate composition according to claim 1, wherein the hydroxyl group-containing (meth) acrylate compound is used in an amount of the dihydroxy group-containing polyoxyalkylene polymer. The molar ratio of the amount of the substance is from 0.1 to 1. An adhesive comprising the photocurable methoxyalkane (meth) acrylate composition according to any one of claims 1 to 8. A hardened material formed by the adhesive of claim 9.