WO2003087181A1

WO2003087181A1 - Visible-light-curable resin composition

Info

Publication number: WO2003087181A1
Application number: PCT/JP2003/005006
Authority: WO
Inventors: Yoke Ai Gan
Original assignee: Henkel Loctite Corporation
Priority date: 2002-04-18
Filing date: 2003-04-18
Publication date: 2003-10-23
Also published as: JP2003313216A; AU2003235274A1

Abstract

A visible-light-curable resin composition which, upon short-time irradiation with light, comes to have a tack-free surface state and which attains a large cure depth. This composition comprises a combination of a photocurable resin ingredient, such as an epoxy acrylate, urethane acrylate, and polyester acrylate, and a photoinitiator ingredient comprising (a) a thioxanthone compound, (b) an amine, and (c) camphorquinone.

Description

Specification

Visible light curable resin composition

Technical field

The present invention relates to a photocurable resin, and more particularly to a resin that can be cured by irradiation with electromagnetic waves in the visible region.

Background art

The photo-curing adhesive is generally of an ultraviolet light curing type, and is cured by irradiating the adhesive with ultraviolet light. However, when an object to be irradiated is damaged by ultraviolet light, for example, for sealing a liquid crystal panel, it is necessary to shield a necessary portion from light or to give special consideration to a spot diameter of a light source. In addition, for example, when light must be irradiated through an opaque material in the ultraviolet region such as polycarbonate, there is a problem that the adhesive cannot be sufficiently hardened.

On the other hand, a visible light-curable adhesive can be easily used for an object to be irradiated which is easily damaged by ultraviolet light without special consideration for a jig or the like. Also, because of its excellent light transmittance, it is possible to cure even through materials that are opaque to ultraviolet light, and it is possible to increase the depth of penetration of light in the adhesive, so a thick adhesive layer Has the advantage that it can be cured.

As the photopolymerization initiator used for the visible light curable adhesive, camphorquinone,

2,4,6-Trimethylbenzoyl diphenylphosphinoxide, benzyl, 4,4-dimethoxybenzyl and the like are known. Among them, camphorquinone having a photosensitive wavelength range of 400 to 500 nm is an excellent initiator, but is expensive.

However, when curing in air, polymerization inhibition is caused by oxygen, so even if the applied adhesive is hardened, curing on the surface is slow and the tackiness of the surface is difficult. Can not be removes. To cure until the surface is no longer sticky, long light irradiation is required, or a large amount of initiator is required. In particular, if a large amount of expensive camphorquinone must be used, cost Disadvantageous. Disclosure of the invention

An object of the present invention is to provide a visible light-curable resin composition which can obtain a tack-free surface state by short-time light irradiation and has a large curing depth.

The present invention is a visible light curable resin composition having a photoinitiator component and a photohardening resin component, wherein the photoinitiator component comprises: (a) a thioxanthone, (b) an amine, and (C) A visible light curable resin composition containing camphorquinone.

Thioxanthone has a maximum absorption at a wavelength of about 380 nm, and is usually used as a UV-powered thione epoxy sensitizer. On the other hand, visible light curable resins containing camphorquinone and amine as initiator components are known, but if short-wavelength light is cut, a tack-free surface is hardly obtained. However, the inventors have found that when thioxanthones are used with camphorquinone phosphoramine compounds, the use of camphorquinone is surprisingly shorter and less than when an initiator system consisting of camphorquinone and an amine compound is used. It was found that even with the amount, a tack-free surface state could be obtained. The reason for this is not necessarily clear and is not limited to theory, but the present inventor speculates that some interaction with thioxanthone and amine compounds may increase the sensitivity of camphurquinone. .

The resin composition of the present invention is used as an adhesive, a sealant, etc., particularly when the object to be irradiated is easily damaged by UV irradiation, such as for sealing a liquid crystal panel, or through an opaque material in the ultraviolet region. It is preferably used for applications that require irradiation, applications that require a thick cured layer of adhesive, and the like.

BEST MODE FOR CARRYING OUT THE INVENTION

The photoinitiator component used in the visible light curable resin composition of the present invention contains thioxanthones, amines, and quinphaquinone as described above.

Thioxanthone has the general formula (I):

It is a compound represented by these. Here, n and m are each independently an integer of 0 to 4, and preferably 0 to 2. R ¹ and R ² independently represent an alkyl group or a halogen. Preferred alkyl groups are straight-chain or branched alkyl groups having up to 8 carbon atoms, and methyl, ethyl, n-propyl and i-propyl are particularly preferred. As the halogen, chlorine is preferable.

Specifically, thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropyl Thioxanthone can be mentioned.

The thioxanthones may be used alone, or two or more compounds may be used together.

Camphor quinone has the formula:

It is a compound represented by these.

As the amine, a known compound usually used as a sensitizer can be used. Preferable amine compounds include, for example, primary amine compounds such as n-butylamine, n-hexylamine, n-octylamine and aniline: N-methylaniline, N-methyl-p-toluidine, dibutylamine, diphenylamine and the like. Secondary amine compounds: Triethylamine, triptylamine, N, N, -dimethylaniline, N, N, dibenzylaniline, N, N'-dimethylaminoethylmethacrylate Relate, p-dimethylaminobenzoic acid, p-dimethylaminobenzoyl, P-dimethylaminobenzoyl, N, Ν'-dimethylanthranic acid methyl ester, ρ-dimethylaminophenethyl alcohol, N, N'-di (A-Hydroxitytyl) Tertiary amine compounds such as 1 p-toluidine, N, N, 1-dimethyl-p-toluidine, N, N, and 1-ethyl-P-toluidine. Also, (meth) acrylic acid esters of alkanolamines such as dimethylaminoethyl methacrylate can be used.

Among these amine compounds, tertiary amine compounds, particularly p-dimethylaminobenzoic acid, and esters thereof (preferably alkyl esters having 1 to 20 carbon atoms) are preferable in consideration of the ease of handling of the compounds, odor and the like. It is preferable to use a tertiary amine compound in which an amino group is directly connected to a benzene ring, such as N, N, di (/ 3-hydroxyshethyl) 1-p-toluidine, N, N, 1-dimethyl-1-p-toluidine. .

The amine compound may be used alone or two or more compounds may be used together.

The mixing ratio of thioxanthones, amines and camphorquinone in the photoinitiator component is such that the total of thioxanthones and camphorquinone is usually 0.2 to 10 parts by weight, preferably 1 to 10 parts by weight of amines. 0.5 to 5 parts by weight, more preferably 1 to 2 parts by weight.

The ratio of thioxanthones to camphorquinone is such that the weight ratio of thioxanthones to camphorquinone is from (5:95) to (95: 5), preferably from (30:70) to (30:70). 80:20), particularly preferably (37:63) to (75:25).

On the other hand, the resin component contained in the composition together with the photoinitiator component may be any resin component that can be hardened by irradiation of light, and may contain a (meth) acrylic oligomer as a main component, if necessary. Preferably containing (meth) acrylic monomer as diluent

(Meth) acrylic oligomers have at least one (meth) acryloyl group, and include, for example, epoxy acrylate, urethane acrylate, Examples thereof include ester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, and melamine acrylate. Of these, epoxy acrylate, urethane acrylate, and polyester acrylate are preferred.

Epoxy acrylate is a compound in which one or more (meth) acrylic acids are introduced into one molecule of an epoxy resin containing [-CH (OH) -CHaO-] derived from an epoxy group. A functional group other than an epoxy residue, for example, an ether group or a hydroxyl group may be contained. Examples of such polyfunctional epoxy acrylates include, for example, bisphenol A-type epoxy acrylate, bisphenol F-type epoxy acrylate, biphenyl-type epoxy acrylate, phenol nopolak-type epoxy acrylate, and cresol novolak-type epoxy Examples thereof include acrylates, epoxy acrylates of aliphatic polyhydric alcohols, and alicyclic epoxy acrylates. Of these, bisphenol A type epoxy acrylate, phenol novolak type epoxy acrylate or cresol novolak type epoxy acrylate is particularly preferable. These are usually polyfunctional (meth) acrylates. The above epoxy acrylates can be used alone or as a mixture. Polyester acrylate is a derivative in which (meth) acrylic acid is ester-bonded to one or more alcohol residues of a polyester obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol. The molecule may contain a functional group other than an ester group, for example, an ether group or a hydroxyl group. Examples of the dibasic acid include maleic acid, fumaric acid, adipic acid, phthalic acid, isophthalic acid, and tetrachlorophthalic acid. Of these, maleic acid, adipic acid, phthalic acid, and isophthalic acid are particularly preferable. . Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, neopentyl glycol, glycerin, and trimethylolpropane. Among them, ethylene glycol, diethylene glycol , Propylene glycol, dipropylene glycol, neopentyldaricol, and trimethylolpropane are preferred. These are usually polyfunctional (meth) ac It is a lylic acid ester. The above polyester acrylates can be used alone or as a mixture.

Urethane acrylate is obtained by reacting polyisocyanate, polyol and hydroxyl-containing (meth) acrylate in a known manner. That is, first, a polyisocyanate is reacted with a polyol to produce a high-molecular-weight polyisocyanate, which is then reacted with a hydroxyl group-containing (meth) acrylate to bond an unsaturated group to a terminal. Alternatively, it is obtained by first reacting a hydroxyl group-containing (meth) acrylate with a polyisocyanate, and then reacting the resulting unsaturated polyisocyanate with a polyol, optionally in the presence of a polyisocyanate. is there.

Examples of the polyisocyanate used herein include, for example, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylenediisocyanate, p —Phenylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 4, 4 '—diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, 1 , 3-xylylene diisocyanate, 1,4-xylylene diisocyanate, and the like.

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and 1,4-butanediol monoacrylate. Examples include (meth) acrylate and methprolactone-modified 2-hydroxyethyl (meth) acrylate.

Further, examples of the polyol include polyethylene glycol, polypropylene dalicol, polytetramethylene ether dalicol and copolymers thereof, ethylene glycol, propylene glycol, 1,4-butanediol, and 2,2′-thiodiethanol. These polyols may be used alone or in combination of two or more.

The main component (meth) acrylic oligomer can be used with only one compound, The above may be used in combination.

Next, the (meth) acrylic monomer used as a diluent may be either a monofunctional compound having one (meth) acrylic group or a multifunctional compound having a plurality of (meth) acrylic groups. .

Monofunctional (meth) acrylic monomers include, for example, butanediol (meth) acrylate, cyclohexyl (meth) acrylate, and dicyclopentyl.

(Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyshethyl (meth) acrylate, N, N-getylaminoethyl (methyl) acrylate, 2-ethoxyhexyl (meth) acrylate, 2 —Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Proprolactone modified 2-hydroxyethyl (meth) acrylate, Isopolnil

(Meth) acrylate, lauryl (meth) acrylate, acryloyl morpholin, N-vinylcaprolactam, nonylphenoxypolyethylene glycol (methyl) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyshetyl (meta) Acrylate, phenoxyhydroxypropyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol

(Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like.

Examples of the polyfunctional (meth) acrylic monomer include 1,4-butanediol di (meth) acrylate, dicyclopentyl di (meth) acrylate, ethylene dalichol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Prolactone-modified dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycol di (meth) acrylate, penyu erythri 1 ^ -tritol (meth) acrylate, polyethylene Glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethyleneglycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (acryloxy) Thiol) isocyanurate, tris (acryloxyshethyl) diisocyanurate, tris (methacryloxyshethyl) isocyanurate, tricyclodecanedimethanol di (meth) acrylate, and the like. These reactive diluents may be used alone or in combination of two or more.

Among these, a monofunctional alkyl (meth) acrylate having a hydroxyl group is preferable. For example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 3-phenyloxy (meth) acrylate, and the like. Hydroxyl pills are preferred.

The mixing ratio of the (meth) acrylic monomer, which is an optional component in the diluent, can be appropriately selected in consideration of the viscosity, the physical properties of the obtained resin, and the like. Usually, 100 parts by weight of the main component (meth) acrylic oligomer is used. 100 parts by weight or less (including 0), preferably 5 parts by weight to 50 parts by weight.

The mixing ratio of the photoinitiator component and the resin component is usually from 0.2 to 15 parts by weight, preferably from 0.5 to 10 parts by weight, preferably from 0.5 to 10 parts by weight, based on 100 parts by weight of the resin component. Preferably it is 1 to 5 parts by weight.

The composition of the present invention may further contain, if necessary, a silane coupling agent, a coloring agent, a surfactant, a storage stabilizer, a plasticizer, a lubricant, an organic or inorganic filler, an antifoaming agent, a leveling agent, and the like. Good.

For example, the silane coupling agent is not particularly limited, but may be aminopropyltriethoxysilane, alphamercaptopropyltrimethoxysilane, alphamethacryloxypropyltrimethoxysilane, τ-daricidoxypropyltrimethylsilane, or SH6062. , SZ6030 (above, Toray Dow Corning, 'Silicon Corp.), KBE903, KBM803 (above, Shin-Etsu Silicone Corp.) and the like.

Example

The components shown in Tables 1 and 4 were mixed to obtain a resin composition. In Examples and Comparative Examples, epoxy acrylate is bisphenol A type epoxy acrylate (UCB Ebecryl 3700), Kayarad UX-6101 (Nippon Dani Pharmaceutical Co., Ltd.) for urethane acrylate, aglycid for silane coupling agent, etyl 4-dimethylaminobenzoate for xip d-pinole trimethinoresilane, and amine for amine.

Each resin composition was applied on a glass plate to a thickness of lmm, and irradiated with light from the surface. The light irradiation time until the tack on the surface of the resin composition disappeared was compared as “tack 'free time”. The shorter the time, the faster the surface stickiness is eliminated, which is preferable. The results are shown in Tables 2 and 5.

In addition, in order to examine the depth of the hardening from the surface, each resin composition was placed in a Teflon cylindrical mold having a diameter of 1.5 cm and a depth of 1 cm, irradiated with light under predetermined conditions, and then taken out of the mold. And the lower unhardened material was wiped off, and the height of the remaining cured resin was compared as “cured through volume”. This height is preferable, as the larger the height, the deeper the stiffness advances from the surface. The results are shown in Tables 3 and 6.

The irradiation light source was adjusted using a medium pressure mercury lamp (Eyegraphics Co. H015-L312) so that the light intensity at 365 nm was 100, 40 and 20 mw / cm ² (U

V meter: Measured at Shio UIT101 @ 365nm).

UV-cut filters were used, L37 (HOYA) and L39 (HOYA).

The spectral characteristic of L37 (HOYA) is 20% transmittance at a wavelength of 365 nm. L39 (HOYA) has a spectral characteristic of 0.5% transmittance at a wavelength of 365 nm. Slave connexion, the L3 ⁹ (HOYA) Fill evening when using an optical wavelength in the UV region is has been little shield sectional, only the visible light is irradiated.

1 Example Example Example Example Example Example Example Example Example

1 2 3 4 5 6 7 1 2 3 4 Epoxy

75 4 75 75 75 ΑΛ 75.44 75 ― 75.44 75.44 Crylate

Peretana

One----One----Crylate

ΗΕΜΑ 1

丄 ΰ · O 丄 O _ O Xo o c

D 丄,, D 丄, O H »P O-丄 D D D Ο Ο 丄丄, ΰ n Q Τ

· D ΰ ο, ΐ

D 丄 ΰ · ο Monomer

Silane cutlet

1.96 1.96 1.96 1.96 1.96 1.96 1.96 1.96 1.96 1.96 1.96 Pulling agent

IRGACURE

4 184

ΤΡΟ 4

Thioxane

0.25 0.5 0.75 1 1.25 1.5 1.75 2

Torn

2 2 2 2 2 2 2 2 2.

Camphor

1.75 1.5 1.25 1 0.75 0.5 0.25

Non J-2

Ki

+100 100 100 100 100 100 loo 1100 100 100 100

ΗΕ モノマー Monomer: Droxityl methacrylate

ΤΡΟ: 2,4,6-tridifunylphosphinoxide

IRGACURE 184 1-H: c diketone

Tack-free time Measurement conditions Example Example Example Example Example Example Example Example 赚, J mm 赚

1 2 3 4 5 6 7 1 2 3 4

365nm

Penal Energy

Le ^ "(seconds)

(mW / an ² )

40 None 1 5 5 5 5 5 5 5 5 * 1) 5-10 5

100 L37 5-10 5-10 5-10 5-10 5-10 10 10 10-15> 40 5-10> 40

40 L37 I 30-35 20-25 10 o-15 10-15 10-15 20-25 20-25 30-35 >> 40 20-25 >> 40

20 L37> 50 30-35 1 20-25 20-25 20-25 30-35 >> 40 45-50 >> 40 n i

100 L39 15-20 15-20 15-20 10 10 15-20 15-20 15-20 * 2) 15-20 * 2)

40 L39 50-55 35-40 20-25 20-25 20-25 25-30 35-40 * 2) 30-35 * 2)

20 L39 >> 50> 45 35-40 35-40 35-40 35-40> 45 >> 45 * 2) * 1) * 2)

* 1) Not measured

* 2) Not measured, but considered to be ">> 40 seconds".

o

1

n i

o

Table 3

Cured through volume Measurement conditions Implementation Implementation Implementation Implementation Implementation Implementation Implementation 赚赚 Puncture J 例 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 2 3 4

1

365 nm irradiation time

Penal, Luyu (mm)

(mW / cm

40 None 20 seconds * 1) * 1) 2.29 * 1) 2.06 * 1) 1.74 * 1) 1.00 2.87

100 L37 30 seconds 4.24 4.24 3.98 * 1) * 1) * 1)

40 L37 30 seconds * 1) * 1) * 1) * 1) * 1) * 1) * 1) * 1) * 1) * 1)

20 L37 50 seconds * 1) * 1) 2.72 * 1)

* 1) 1.74 * 1) 1.23 * 1)

40 L39 30 seconds * 1) 3.00 * 1) 2.72 * 1) * 1) * 1) 1.17 * 1)

* 1) Not measured. Ura 0 0

O C

Dimension 00

ni

Table 4

n i

o

Example supplement measurement condition J

8 5

365nm

Penaru

Le (seconds)

(mW / cm ² )

100 L37 5 15-20

40 L37 25-30 40

100 L39> 40 Table 6

Cured through volume

As is clear from the above, various changes can be made to the photocurable resin component as long as the gist of the present invention is not deviated. Therefore, the form described here is an example, and the scope of the present invention described in the claims is not limited thereto.

Industrial applicability

According to the present invention, a tack-free surface state can be obtained by short-time light irradiation.

A visible light curable resin composition having a large curing depth can be provided.

Claims

The scope of the claims

1. A visible light curable resin composition having a photoinitiator component and a photocurable resin component.

The photoinitiator component,

(a) thioxanthones,

(b) amines, and

(c) Camphor quinone

A visible light-curable resin composition comprising:

2. The photoinitiator component comprises: (b) 1 part by weight of an amine,

The composition according to claim 1, wherein the total of (a) thioxanthones and (c) camphorquinone is in a ratio of 0.2 to 10 parts by weight.

3. The photoinitiator component comprises: (b) 1 part by weight of amines,

The composition according to claim 1, wherein the total of (a) thioxanthones and (c) camphorquinone is 0.5 to 5 parts by weight.

4. The composition according to claim 1, wherein the ratio of thioxanthone to camphorquinone is (5:95) to (95: 5) by weight ratio of thioxanthone: camphorquinone.

5. The composition according to claim 1, wherein the ratio of thioxanthones to camphorquinone is from 30:70 to (80:20) by weight ratio of thioxanthone: camphorquinone.

6. The thioxanthones are thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-dichloromouth thioxanthone, 2-chlorothioxanthone 2. The composition according to claim 1, wherein the composition is selected from the group consisting of xanthone, 2,4-dimethylthioxanthone, 2,4-dimethylthioxanthone and 2,4-diisopropylthioxanthone.

7. The composition according to claim 1, wherein the amines are selected from the group consisting of p-dimethylaminobenzoic acid and esters thereof.

8. The composition according to claim 1, wherein the mixing ratio of the photoinitiator component and the photohardening resin component is 0.2 to 15 parts by weight, based on 100 parts by weight of the resin component. Composition.

9. The composition according to claim 1, wherein the mixing ratio of the photoinitiator component and the photocurable resin component is 100 to 100 parts by weight of the resin component, and the photoinitiator component is 0.5 to 10 parts by weight. .

10. The composition according to claim 1, wherein the photocurable resin component contains (meth) acrylolygomer as a main component, and may contain a (meth) acrylic monomer as a diluent.

1 1. The (meth) acrylic oligomer is selected from epoxy acrylate, urethane acrylate, polyester acrylate, polybutadiene acrylate, polyacrylate, polyether acrylate, silicone resin acrylate, and melamine acrylate. The composition according to claim 10, comprising at least one member selected from the group consisting of:

12. The composition according to claim 10, wherein the (meth) acrylic oligomer is at least one selected from the group consisting of epoxy acrylate, urethane acrylate, and polyester acrylate.

1 3. The (meth) acrylic monomer is a monofunctional (meth) having a hydroxyl group. 10. The composition according to claim 10, which is an alkyl acrylate.

4. The composition according to claim 1, which comprises a 4 thin coupling agent.