JP2003026774A - Thermosetting composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting composition which can form a cured film (a coating film) improved in tackiness while retaining adhesiveness to various substrates, especially a thermosetting composition which contains an oxetane compound such as an oxetane-ring-containing non-acrylic compound. SOLUTION: This thermosetting composition contains (A) an oxetane-ring- containing non-acrylic compound, (B) a fluoroalkyl (meth)acrylate or its polymer, (C) an oxirane-ring-containing non-acrylic compound, (D) a polyol compound, and (E) a thermal cationic polymerization initiator.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermosetting composition (in particular, a thermosetting composition containing an oxetane compound such as an oxetane ring-containing non-acrylic compound). Such a thermosetting composition can form a cured film (coating film) excellent in transparency, heat resistance, adhesion, etc. on the surface of a substrate such as metal (iron etc.), plastic, etc. It is useful in applications, coatings, printing, etc.

[0002]

2. Description of the Related Art In a conventional thermosetting composition (for example, a thermosetting composition containing an oxetane compound such as an oxetane ring-containing non-acrylic compound), a cured film (coating) formed on the surface of a substrate is used. In order to improve the tackiness of the (membrane), a low molecular weight compound such as a surfactant is often added. However, in this case, there is a problem that the adhesiveness between the cured film (coating film) and the substrate is lowered.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a thermosetting composition capable of forming a cured film (coating film) which has improved tackiness and retains adhesiveness to various substrates ( In particular, it is an object to provide a thermosetting composition comprising an oxetane compound such as an oxetane ring-containing non-acrylic compound.

[0004]

The object of the present invention is (A)
Oxetane ring-containing non-acrylic compound, (B) (meth)
Acrylic acid fluoroalkyl ester or polymer thereof, (C) oxirane ring-containing non-acrylic compound,
It is solved by a thermosetting composition containing (D) a polyol compound and (E) a thermal cationic polymerization initiator. In addition, in this invention, (meth) acrylic acid means acrylic acid or methacrylic acid.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Oxetane ring-containing non-acrylic compound The oxetane ring-containing non-acrylic compound that is the component A of the thermosetting composition of the present invention includes 1 to 4 oxetane rings in the molecule. A compound containing () which is not bound to (meth) acrylic acid (eg, does not form an ester) is preferably used.

Of these, the non-acrylic compounds containing one oxetane ring in the molecule are preferably monooxetane compounds represented by the formula (1). (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

[0007]

[Chemical 1]

In the formula (1), R ¹ is a hydrogen atom, or the number of carbon atoms such as methyl group, ethyl group, n- (or iso-) propyl group, n- (or iso-, sec-) butyl group. 1 to 6 represents an alkyl group, among which a hydrogen atom,
A methyl group and an ethyl group are preferable, and among them, a methyl group and an ethyl group are more preferable. Examples of the monooxetane compound as described above include 3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, and the like. Among them, 3-methyl-3 -Hydroxymethyl oxetane and 3-ethyl-3-hydroxymethyl oxetane are preferred.

As the non-acrylic compound containing two oxetane rings in the molecule, a bisoxetane compound represented by the formula (2) is preferably mentioned. (In the formula, R ² ,
R ³ is the same as R ¹ above, and A represents an alkylene group (which may form an unsaturated bond, an aliphatic hydrocarbon ring, or an aromatic ring inside the carbon chain) when x = 1. Represent, x = 2
In the case of an integer of ~ 12, it represents an ethylene group. Also, x is 0
Represents an integer of -12. )

[0010]

[Chemical 2]

In the compound represented by the formula (2),
R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms and may be the same or different. Among the compounds, those in which R ² and R ³ are the same as each other are preferable, but among them, those in which R ² and R ³ are the same as each other and are either a hydrogen atom, a methyl group or an ethyl group are preferable, Among them, those in which R ² and R ³ are the same and are either methyl group or ethyl group are more preferable.

Preferred examples of the compound represented by the formula (2) include the following. Monoether bisoxetane where x = 0 and diether bis where A is an alkylene group (which may contain an unsaturated bond, an aliphatic hydrocarbon ring or an aromatic ring in the carbon chain). Oxetanes x = an integer of 2 to 12, and A is an ethylene group, a polyether bisoxetane

Examples of the above-mentioned monoether bisoxetanes include bis [(3-ethyl-3-oxetanyl) methyl] ether and bis [(3-methyl-3-oxetanyl) methyl] ether. Monoether bisoxetanes are, for example, 3-alkyl-3
-Hydroxymethyl oxetane is synthesized by reacting p-toluenesulfonyl chloride of 3-alkyl-3-hydroxymethyl oxetane.

In the above-mentioned dietherbisoxetanes, the alkylene group (X) may form an unsaturated bond, an aliphatic hydrocarbon ring or an aromatic ring inside the carbon chain. That is, examples of the alkylene group include alkylene groups having 1 to 12 carbon atoms such as an ethylene group, a tetramethylene group, and a hexamethylene group. Aliphatic hydrocarbon rings (cyclohexane ring, etc.) inside the carbon chain such as an alkylene group having 4 to 6 carbon atoms forming a saturated bond (carbon-carbon double bond, etc.) and the group represented by formula (4). 2 to 6 carbon atoms forming
C2-C6 (rings, etc.) forming an aromatic ring (benzene ring, etc.) inside the carbon chain of an alkylene group (excluding carbon atoms in the ring), a xylylene group and a group represented by the formula (5). (Excluding the carbon atoms of) (including each isomer of o-, m-, p-, etc.) and the like.

[0015]

[Chemical 3]

Examples of diether bisoxetanes include 1,2-bis [(3-ethyl-3-oxetanyl) methoxy] ethane and 1,4-bis [(3-ethyl-
3-oxetanyl) methoxy] butane, 1,6-bis [(3-ethyl-3-oxetanyl) methoxy] hexane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxy] -2-butene, or , 1,4- [bis (3-
Ethyl-3-oxetanylmethoxy) methyl] cyclohexane, 1,4- [bis (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4,4 '-[bis (3-ethyl-3-oxetanylmethoxy) methyl ] Biphenyl, 4,4 '-[bis (3-methyl-3-oxetanylmethoxy) methyl] biphenyl and the like can be mentioned. Diether bisoxetanes are synthesized, for example, by reacting a corresponding dibromide (xylylene dibromide, ethylene dibromide, etc.) with 3-alkyl-3-hydroxymethyloxetane.

Examples of the above-mentioned polyether bisoxetanes include diethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, triethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, tetra Examples thereof include ethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether. Polyether bisoxetanes are
For example, it is synthesized by reacting a corresponding polyethylene glycol (diethylene glycol, triethylene glycol, tetraethylene glycol, etc.) with p-toluenesulfonyl chloride of 3-alkyl-3-hydroxymethyloxetane.

Preferred examples of the non-acrylic compound containing 3 or 4 oxetane rings in the molecule include compounds represented by the formula (6). (In the formula, R ⁴ is the same as the above R ¹ , Z ¹ represents a trivalent or tetravalent group, n is 3 or 4. Z is a trivalent group which may have a substituent. Or a tetravalent hydrocarbon group, a trivalent or tetravalent group represented by the formula (7), or a trivalent or tetravalent group represented by the formula (8).
In addition, Y ¹ and Y ² are trivalent or tetravalent hydrocarbon groups which may have a substituent, and p and q are 3 or 4. )

[0019]

[Chemical 4]

[0020]

[Chemical 5]

[0021]

[Chemical 6]

Of the above Z, the trivalent or tetravalent hydrocarbon group which may have a substituent is, for example, one represented by the formula (9):
To trivalent or tetravalent aliphatic hydrocarbon groups having 1 to 12 carbon atoms represented by (11) and the like. (In the formula, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

[0023]

[Chemical 7]

Among the above Zs, examples of the trivalent or tetravalent group represented by the formula (7) include those in which Y ¹ is a trivalent or tetravalent aromatic hydrocarbon group. Examples of Y ¹ include a trivalent aromatic hydrocarbon group represented by the following formula.

[0025]

[Chemical 8]

Among the above Z, the trivalent or tetravalent group represented by the formula (8) is, for example, an aliphatic or aromatic hydrocarbon group in which Y ² is trivalent or tetravalent. Examples of Y ² include a trivalent aliphatic or aromatic hydrocarbon group represented by the following formula.

[0027]

[Chemical 9]

A non-acrylic compound containing 3 or 4 oxetane rings in the molecule is represented by the formula (6):
R ⁴ is the above alkyl group, Z is a trivalent aliphatic hydrocarbon group having 1 to 12 carbon atoms represented by the formula (9), R
^It is preferable that ⁴ is the alkyl group and Z is a trivalent or tetravalent group represented by the formula (7). Further, in the formula (6), R ⁴ is an ethyl group, Z is a trivalent aliphatic hydrocarbon group having 1 to 12 carbon atoms represented by the formula (9), and R ⁵ is an ethyl group. More preferably, R ⁴ is an ethyl group, Z is a trivalent or tetravalent group represented by the formula (7), and is represented by the following formula, and q = 3: .

[0029]

[Chemical 10]

In the molecule represented by the above formula (6), 3
Alternatively, the non-acrylic compound containing four oxetane rings is synthesized from 3-alkyl-3-hydroxymethyloxetane as a starting material in the same manner as the bisoxetane compound represented by the formula (2).

(B) Fluoroalkyl ester of (meth) acrylic acid or polymer thereof In the fluoroalkyl ester of (meth) acrylic acid or polymer thereof which is the component B of the thermosetting composition of the present invention, fluoroalkyl (meth) acrylate is used. Preferable examples of the ester include esters of (meth) acrylic acid and fluoroalkyl alcohol. As this fluoroalkyl group, a trifluoroethyl group (—CH ₂ C
F _3), tetra-fluoropropyl group _(-CH 2 (C
F ₂ ) ₂ H), octafluoropentyl group (-CH
1 to 12 carbon atoms (especially 1 to 5) such as ₂ (CF ₂ ) ₄ H)
Preferred are those in which the alkyl group of is substituted with two or more fluorine atoms. Specific examples of the (meth) acrylic acid fluoroalkyl ester include trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, and the like.

The above (meth) acrylic acid fluoroalkyl ester preferably further contains an oxetane ring-containing (meth) acrylic acid ester or an oxirane ring-containing (meth) acrylic acid ester. The content ratio is
5 to 100 parts by weight of (meth) acrylic acid fluoroalkyl ester, and further 10 to 80 parts by weight based on 100 parts by weight of the total of the oxetane ring-containing (meth) acrylic acid ester and the oxirane ring-containing (meth) acrylic acid ester. Is preferred. In addition, oxetane ring included (meta)
The acrylic acid ester and the oxirane ring-containing (meth) acrylic acid ester may be contained at the same time, and in that case, the ratio of both is not particularly limited.

Examples of the oxetane ring-containing (meth) acrylic acid ester include (meth) acrylic acid and an oxetane ring-containing alcohol (particularly, a monooxetane compound represented by the above formula (1); a 3-oxetanylmethanol compound).
And an ester thereof are preferred. Specifically, as an oxetane ring-containing (meth) acrylic acid ester, (meth) acrylic acid (3-ethyl-3-oxetanyl) methyl, (meth) acrylic acid (3-methyl-3-oxetanyl) methyl, (meth ) 3-Oxetanylmethyl acrylate and the like can be mentioned. Among them, (3-ethyl-3-oxetanyl) methyl methacrylate and methacrylic acid (3-
Methyl-3-oxetanyl) methyl is preferred.

The oxirane ring-containing (meth) acrylic acid ester is preferably an ester of (meth) acrylic acid and an oxirane ring-containing alcohol. The oxirane ring-containing alcohol has an alkyl group having 1 to 4 (preferably 1 to 2) carbon atoms, and the alkyl group has an oxiranyl group as a substituent, or a cycloalkyl group having 5 carbon atoms. ~
Preferred are cycloalkyl alcohols having 12 (preferably 5 to 7) and a part of carbon atoms of the cycloalkyl group form an oxirane ring. In this case, the alkyl group or cycloalkyl group may be further substituted with a halogen atom or the like. Specific examples of the oxirane ring-containing alcohol include glycidyl alcohol and 3,4
-Epoxy cyclohexyl methanol and the like.
That is, as the oxirane ring-containing (meth) acrylic acid ester, specifically, glycidyl (meth) acrylate,
Examples thereof include (3,4-epoxycyclohexyl) methyl (meth) acrylate.

The polymer of the fluoroalkyl ester of (meth) acrylic acid, which is the component B of the thermosetting composition of the present invention, is the polymer of the fluoroalkyl ester of (meth) acrylic acid (that is, poly (meth) acrylate). , Polystyrene-reduced number average molecular weight of 1000-
It is preferably 80,000, more preferably 2,000 to 50,000. This polymer may be one prepared by radically polymerizing the above-mentioned (meth) acrylic acid fluoroalkyl ester in the presence of an initiator such as azoisobutyronitrile in the component A, and the components A, C, D, and It may be prepared by similarly radically polymerizing in a mixture of component E. In the former case, the obtained polymer (component A, B
(Including components) can be directly used for preparing the composition of the present invention, and in the latter case, the obtained polymer (including components A to E) is obtained.
Can be directly used as the composition of the present invention. Also,
The (meth) acrylic acid fluoroalkyl ester polymer may be obtained by similarly radically polymerizing in another solvent. When the (meth) acrylic acid fluoroalkyl ester further contains an oxetane ring-containing (meth) acrylic acid ester or an oxirane ring-containing (meth) acrylic acid ester, the polymer (copolymer) may be similarly prepared. it can.

(C) Non-acrylic compound containing oxirane ring As the non-acrylic compound containing oxirane ring which is the component C of the thermosetting composition of the present invention, 3,4-epoxycyclohexylmethyl-3 ', 4'- Epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,6-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4 -Vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis ( 3,4-epoxycyclohexane) Dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4
-Epoxycyclohexanecarboxylate), epoxidized tetrahydrobenzyl alcohol, lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-
Epoxy cyclohexane carboxylate, lactone-modified epoxidized tetrahydrobenzyl alcohol, cyclohexene oxide, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated Alicyclic epoxy compounds such as bisphenol F diglycidyl ether and brominated bisphenol S diglycidyl ether,

1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, aliphatic poly Polyether polyol polyglycidyl ether obtained by adding one or more alkylene oxides to polyhydric alcohol, aliphatic long-chain dibasic acid diglycidyl ester, aliphatic higher alcohol monoglycidyl ether, higher fatty acid glycidyl ester, butyl epoxystearate, Epoxy Aliphatic epoxy compounds such as octyl stearate,

Bisphenol A diglycidyl ether,
Aromatic epoxy compounds such as bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, phenols (phenol, cresol, butylphenol, etc.) and polyether alkylene alcohol monoglycidyl ether, epoxidized novolac resin, epoxidized soybean oil , Epoxidized linseed oil and the like.

Examples of commercial products of the aliphatic epoxy compounds include UVR-6110, UVR-6128 (above manufactured by UCC), Celoxide 2021, Celoxide 2081, Celoxide 3000 (above produced by Daicel Chemical Industries) and the like.

(D) Polyol compound As the polyol compound which is the D component of the thermosetting composition of the present invention, a polyhydric alcohol having a valence of 3 or more (trimethylolpropane, glycerin, pentaerythritol, sorbitol, sucrose, etc.) is used. Cyclic ether compounds (ethylene oxide (EO), propylene oxide (PO),
(Butylene oxide, tetrahydrofuran, etc.), a polyether polyol obtained by modification with a lactone, a polylactone polyol obtained by modifying a polyhydric alcohol having a valence of 3 or more with a lactone, and a polyhydric alcohol having a valence of 3 or more. A polyester polyol obtained by modifying with a polyester composed of a basic acid and a diol is preferable.

Specific examples of the polyether polyol include EO-modified trimethylolpropane, PO-modified trimethylolpropane, tetrahydrofuran-modified trimethylolpropane, EO-modified glycerin, PO-modified glycerin, tetrahydrofuran-modified glycerin, EO-modified pentaerythritol, PO. Examples include modified pentaerythritol, tetrahydrofuran-modified pentaerythritol, EO-modified sorbitol, PO-modified sorbitol, EO-modified sucrose, PO-modified sucrose and the like.

As the polylactone polyol,
Specific examples thereof include a caprolactone-modified trimethylolpropane, a caprolactone-modified glycerin, a caprolactone-modified pentaerythritol, and a caprolactone-modified sorbitol.

Among these polyol compounds, EO-modified trimethylolpropane, PO-modified trimethylolpropane, caprolactone-modified trimethylolpropane,
PO-modified glycerin, PO-modified sorbitol, and caprolactone-modified glycerin are preferable.

Commercially available products of the polyol compound include, for example, Sannix TP-400 and Sannix SP-7.
50, Sannix GP-60, Sannix GP-2
50, Sannix GP-400, Sannix GP-
400, Sannix GP-1000 (above, Sanyo Kasei), TMP-3 Glycol, PNT-4 Gly
col, EDA-P-4, EDA-P-8 (all manufactured by Nippon Emulsifier), G-300, G-400, G-700, T.
-400, EDP-450, SP-600, SC-80
0 (above, Asahi Denka), TONE0301, TONE0
305, TONE0310 (above, manufactured by Union Carbide), Praxel 303, Praxel 305, Praxel 308 (above manufactured by Daicel Chemical Industries), and the like.

(E) Thermal Cationic Polymerization Initiator The thermal cationic polymerization initiator used in the present invention is at least one selected from compounds capable of initiating ring opening of an oxetane ring and cationic polymerization by heat (heating). Compounds of

Examples of such compounds are shown below.
Various onium salts such as those represented by the formula (12)
Quaternary ammonium salt (in the formula, R⁶~ R⁹Has 1 to 2 carbon atoms
0 alkyl group, C5-12 cycloalkyl group,
C3-C12 alkenyl group, C6-C12 ant
Group, aralkyl group having 7 to 12 carbon atoms, or 1 carbon atom
~ 20 alkoxy groups, which may be the same or different from each other.
Or may have a substituent. Also, R⁶~
R⁹Two of them are bonded together to form N, P, O, or
It may form a heterocycle containing an S atom. X^-Is against
Indicates on, BF_Four ^-, AsF₆ ^-, SbF₆ ^-, SbC
l₆ ^-, (C₆F_Five)_FourB^-, SbF_Five(OH)^-, HSO_Four ^-,
p-CH₃C₆H_FourSO₃ ^-, HCO₃ ^-, H₂PO_Four ^-, CH₃
CO₂ ^-, Halogen ion (Cl^-, Br^-, I^-Etc., etc
Chosen from. ),

[0047]

[Chemical 11]

A phosphonium salt represented by the formula (13) (in the formula, R ^{6 to} R ⁹ and X ⁻ are the same as above);

[0049]

[Chemical 12]

The sulfonium salt represented by the formula (14) (in the formula, R ^{6 to} R ⁸ and X ⁻ are the above R ^{6 to} R ⁹ and X ⁻ , respectively).
Is the same as. Ar represents an aryl group which may have a substituent. ), A sulfonium salt represented by the formula (15) (in the formula, R ^{6 to} R ⁷ , X ⁻ , and Ar are the same as the above R ^{6 to} R ⁹ , X ⁻ , and Ar, respectively) and a formula ( 1
6) sulfonium salt (in the formula, R ^{6 to} R ⁹ ,
X ⁻ and Ar are the same as above. ) And the like.

[0051]

[Chemical 13]

[0052]

[Chemical 14]

[0053]

[Chemical 15]

Examples of the quaternary ammonium salt include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogensulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, N, N-dimethyl-N-benzylanilinium hexafluoroantimonate, N, N-dimethyl-N-
Benzylanilinium tetrafluoroborate, N, N
-Dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl-N-benzyltrifluoromethanesulfonate, N, N-dimethyl-N-
Specific examples thereof include (4-methoxybenzyl) pyridinium hexafluoroantimonate and N, N-diethyl-N- (4-methoxybenzyl) toludinium hexafluoroantimonate.

Specific examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsinate, tris (4-methoxyphenyl) sulfonium hexafluoroarsinate, diphenyl. (4-phenylthiophenyl) sulfonium hexafluoroarsinate,

Adeka Opton SP-150 (hereinafter Asahi Denka Co., Ltd.), Adeka Opton SP-170, Adeka Opton CP-66, Adeka Opton CP-77, San-Aid SI-60L (Sanshin Chemical Co., Ltd.), San-Aid SI-
80L, Sun-Aid SI-100L, CYRACUR
EUVI-6974 (hereinafter Union Carbide), CYRACURE UVI-6990,

UVI-508 (hereinafter referred to as General Electric), UVI-509, FC-508 (hereinafter referred to as Minnesota Mining and Manufacturing), FC-509, and CD-1010 (hereinafter referred to as Cerstomer). ), CD-1011, products of CI series (CI-2639, etc.) (manufactured by Nippon Soda), and the like.

Further, in the present invention, the diazonium salt represented by the formula (17) (in the formula, Ar and X are the same as defined above) and the iodonium salt represented by the formula (18) (the R in the formula). ^{6 to} R ⁷ and X ⁻ are the same as those described above.) Can also be used as the thermal cationic polymerization initiator.

[0060]

[Chemical 16]

[0061]

[Chemical 17]

As the diazonium salt, AMERI
CURE (American Can), ULTRASET
(Manufactured by Asahi Denka) and the like. The iodonium salt may be diphenyliodonium hexafluoroarsinate, bis (4-chlorophenyl) iodonium hexafluoroarsinate, bis (4-bromophenyl) iodonium hexafluoroarsinate, phenyl (4-methoxyphenyl) iodonium hexafluoro. Alcinate, UV-9310C (manufactured by Toshiba Silicone), Photoinitiator 2074 (manufactured by Rhone Poulin), UVE series products (manufactured by General Electric), FC series products (manufactured by Minnesota Mining and Manufacturing), etc. .

[Thermosetting composition] (A) oxetane ring-containing non-acrylic compound, (B) (meth) acrylic acid fluoroalkyl ester or polymer thereof, (C) oxirane ring-containing non-acrylic compound, (D) In the thermosetting composition of the present invention comprising a polyol compound and (E) a thermal cationic polymerization initiator, the component B is 5 to 80 parts by weight, further 10 to 50 parts by weight, relative to 100 parts by weight of the component A. Parts by weight, C component is 200 to 10,000 parts by weight, and further 50
0 to 2500 parts by weight, component D is preferably contained in the proportion of 200 to 10,000 parts by weight, and further preferably in the proportion of 500 to 2000 parts by weight. Also, the E component is the A component,
0.1 to 1 with respect to the total of B component, C component, and D component
The content is preferably 0% by weight, more preferably 0.4 to 5% by weight. In addition, the (meth) acrylic acid fluoroalkyl ester of the component B or its polymer is constituted (meth).
As described above, the fluoroalkyl acrylate ester preferably further contains an oxetane ring-containing (meth) acrylic acid ester or an oxirane ring-containing (meth) acrylic acid ester.

The thermosetting composition of the present invention can be obtained by mixing and dissolving the above-mentioned components A to E. The temperature at this time is a temperature at which thermal cationic polymerization is not caused, for example,
It is preferably less than 50 ° C, more preferably 10 to 30 ° C. Usually prepared at room temperature. Further, the pressure and atmosphere at the time of preparation are not particularly limited, and normally atmospheric pressure and atmospheric air may be used. B
When the component is the above polymer, it is particularly preferable to prepare the polymer by preparing the polymer in the component A and then mixing the other components.

The thermosetting composition of the present invention can be made into a cured product (for example, cured film) by heating. For example,
After the thermosetting composition is applied to the surface of the substrate, it is heated to open the oxetane ring and the oxirane group and to perform cationic polymerization to form a cured film (coating film). In addition, a continuous cured film (coating film) combined with the production of substrate moldings such as film molding and extrusion molding.
Can also be formed. The cured film (coating film) thus obtained has improved tackiness, good adhesion to various substrates, and excellent transparency.

When the component B is a monomer such as (meth) acrylic acid fluoroalkyl ester, it is preferable that the polymer is produced by radical polymerization in advance and then cured to obtain a cured product. Therefore, as the B component, in addition to the (meth) acrylic acid fluoroalkyl ester polymer, particularly (meth) acrylic acid fluoroalkyl ester, an oxetane ring-containing (meth) acrylic acid ester or an oxirane ring-containing (meth) acrylic acid ester is also used. Polymers (copolymers) containing are preferred.

The temperature for heating the thermosetting composition is a temperature at which the composition can maintain a molten state, that is, 50 ° C. or higher,
Further, it is preferably 50 to 200 ° C., particularly preferably 60 to 160 ° C. The heating time varies depending on the composition of the composition and the heating conditions, but is usually 1 minute to 50 hours, preferably 5 minutes to 10 hours, and more preferably 10 minutes to 5 hours. Further, the pressure during heating is not particularly limited as long as the above-mentioned molten state can be maintained, and may be normal pressure, increased pressure, or reduced pressure. The atmosphere during heating is preferably dry (particularly under dry air).

The base material is not particularly limited.
For example, iron, stainless steel, aluminum, other metals, alloys, rubber, plastic, paper, wood, glass,
Cloth, cement mortar, concrete, ceramics (including films, plates, molded parts and other shaped articles)
Etc. are mentioned as a base material. The UV-curable composition may be applied to the surface of the substrate by a commonly used method such as brush coating, spin coating, spray coating, casting, dipping, roll coating, screen printing or gravure printing.

The thermosetting composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Examples of additives include compounds having two or more hydroxyl groups in the molecule, thermoplastic polymer compounds, fillers, colorants, stabilizers (heat stabilizers, weather resistance improvers, etc.), polymerization inhibitors, leveling. Agents, wettability improvers, anti-sagging agents, precipitation inhibitors, surfactants, UV absorbers, coupling agents, extenders, viscosity modifiers, flame retardants, antioxidants, discoloration inhibitors, antibacterial agents, antifungal agents Agent, anti-aging agent, antistatic agent, conductivity imparting agent, plasticizer, lubricant, foaming agent, defoaming agent,
Examples thereof include a release agent and an adhesiveness-imparting agent.

[0070]

EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples. The cured film formed on the surface of the base material was evaluated by the following method.

(1) Contact angle of water to cured film: CA-
Using an X-type contact angle meter (Kyowa Interface Science), temperature 23
The measurement was performed in an atmosphere of ° C and a humidity of 50%. (2) Cross-cut test: glass (100 × 100 × 1.7 m
m), an aluminum plate (100 × 100 × 1.0 mm), a stainless steel plate (100 × 100 × 1.0 mm), J
It was evaluated by the method specified in ISK5400. (3) Surface tackiness of the cured film: judged by a finger touch test. (4) Transparency of cured film: visually determined. (○: colorless and transparent)

Reference Example 1 [Synthesis of bis [(3-ethyl-3-oxetanyl) methyl] ether] 2 L in internal volume equipped with a thermometer, a stirrer, a rectification column, a condenser, a nitrogen gas introducing pipe, and a dropping funnel. In a (liter) four-necked flask, 511.1 g (4.4 mol) of 3-ethyl-3-hydroxymethyloxetane, 222.6 g (2.2 mol) of triethylamine, and toluene 1
Put 100g, under nitrogen gas atmosphere, the reaction temperature 10 ℃
229.1 g (2.0 mol) of methanesulfonyl chloride (hereinafter referred to as MSC) was added dropwise while maintaining the temperature below. Then, the reaction was continued at room temperature for 2 hours, and the generated precipitate was removed by filtration.

The precipitate was washed with 100 g of toluene, the washing solution and the filtrate were combined and returned to the reactor, and 32.2 g of tetra-n-butylammonium bromide was added.
At 0 ° C, 60.0 g (1.5
Mol) was added in 1 hour. After the addition was completed, the reaction was continued at the same temperature for 2 hours and further at 70 ° C. for 5 hours. After the reaction was completed, 300 g of pure water was added to separate the organic layer. Then, from this organic layer, the desired bis [(3-ethyl-3-
Oxetanyl) methyl] ether 307.5 g (1.4
(Mol) was separated by distillation (200 ° C./6 mmHg). The purity (area percentage) by gas chromatography analysis of this product was 98.9%.

Example 1 [Production of methacrylic acid fluoroalkyl ester polymer] Bis [(3-ethyl-3-oxetanyl) methyl]
To 100 parts by weight of ether, 16.5 parts by weight of trifluoroethyl methacrylate (biscoat 3FM; manufactured by Osaka Organic Chemical Co., Ltd.) as a methacrylic acid fluoroalkyl ester,
As the oxirane ring-containing methacrylic acid ester, 16.5 parts by weight of Cyclomer M-100 (manufactured by Daicel Chemical Industries, Ltd.) was mixed, and further, azoisobutyronitrile was mixed so as to be 1 mol% with respect to these methacrylic acid esters. Polymerization solution F1 was reacted by reacting at 80 ° C. for 7 hours under a nitrogen atmosphere.
Got The number average molecular weight (in terms of polystyrene) of the produced polymer was 28,000.

[Preparation of Thermosetting Composition and Evaluation of Cured Film] Polymerization solution F1 (containing components A and B)
12 parts by weight of UVR-6128 (UCC as C component)
100 parts by weight of Plaxel 303 as D component
50 parts by weight (manufactured by Daicel Chemical), SI component as E
A thermosetting composition was prepared by mixing 6.5 parts by weight of 60 L (manufactured by Sanshin Kagaku). Next, the composition was cast at room temperature on a glass plate (100 mm × 100 mm × 1.7 mm) with a spacer attached, and then heated at 110 ° C. for 1 hour to obtain a cured film. Table 1 shows the evaluation results of the obtained cured film.

Comparative Example 1 [Production of Methacrylic Acid Fluoroalkyl Ester Polymer] The oxirane ring-containing methacrylic acid ester was used in an amount of 3 without using methacrylic acid fluoroalkyl ester.
Polymerization solution F2 was obtained by the same reaction as in Example 1 except that the amount was changed to 2.7 parts by weight. The number average molecular weight (in terms of polystyrene) of the produced polymer was 35,000.

[Preparation of thermosetting composition and evaluation of cured film] The thermosetting property was the same as in Example 1 except that the polymerization solution was replaced with 12 parts by weight of the polymerization solution F2 (containing no component B). A composition was prepared. Then, using this composition, a cured film was obtained in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained cured film.

Example 2 [Production of methacrylic acid fluoroalkyl ester polymer] Example 1 except that the methacrylic acid fluoroalkyl ester was replaced with 16.5 parts by weight of tetrafluoropropyl methacrylate (Biscoat 4FM; manufactured by Osaka Organic Chemical Co., Ltd.)
Polymerization solution F3 was obtained by reacting in the same manner as. The number average molecular weight of the produced polymer (in terms of polystyrene) is 38,000.
Met.

[Preparation of thermosetting composition and evaluation of cured film] The polymerization solution was replaced with 12 parts by weight of the polymerization solution F3 (containing the components A and B), and the component E was replaced with SI-80L.
Example 3 except that 6.5 parts by weight (manufactured by Sanshin Kagaku) was used.
A thermosetting composition was prepared in the same manner as in. Then, using this composition, a cured film was obtained in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained cured film.

Example 3 [Production of methacrylic acid fluoroalkyl ester polymer] Except that the methacrylic acid fluoroalkyl ester was replaced with 16.5 parts by weight of teoctafluoropentyl methacrylate (Biscoat 8FM; made by Osaka Organic Chemical). Polymerization solution F4 was obtained by reacting in the same manner as in 1. The number average molecular weight (polystyrene conversion) of the produced polymer is 3500.
It was 0.

[Preparation of Thermosetting Composition and Evaluation of Cured Film] The polymerization solution was replaced with 12 parts by weight of the polymerization solution F4 (containing the components A and B), and the component D was replaced by the praxel 30.
5 (manufactured by Daicel Chemical Industries) in place of 50 parts by weight, the E component was replaced by SI
A thermosetting composition was prepared in the same manner as in Example 1 except that 6.5 parts by weight of -100 L (manufactured by Sanshin Chemical Industry Co., Ltd.) was used. Then, using this composition, a cured film was obtained in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained cured film.

Example 4 [Preparation of thermosetting composition and evaluation of cured film] 24 parts by weight of the above polymerization solution F1 and UVR-6128 as a C component.
90 parts by weight (made by UCC), Praxel 3 as D component
50 parts by weight of 03 (manufactured by Daicel Chemical) and S as E component
-100 parts by weight of I-100L (manufactured by Sanshin Kagaku) were mixed,
A thermosetting composition was prepared. Then, using this composition, a cured film was obtained in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained cured film.

Example 5 [Preparation of thermosetting composition and evaluation of cured film] A polymerization solution was prepared by using the polymerization solution F2 (containing the components A and B) 24.
A thermosetting composition was prepared in the same manner as in Example 4 except that parts by weight were replaced. This composition is then used to prepare Example 1.
A cured film was obtained in the same manner as in. Table 1 shows the evaluation results of the obtained cured film.

Example 6 [Preparation of thermosetting composition and evaluation of cured film] A polymerization solution was used as the polymerization solution F3 (containing components A and B) 24.
A thermosetting composition was prepared in the same manner as in Example 4 except that parts by weight were replaced. This composition is then used to prepare Example 1.
A cured film was obtained in the same manner as in. Table 1 shows the evaluation results of the obtained cured film.

Example 7 [Preparation of thermosetting composition and evaluation of cured film] The polymerization solution was replaced with the above-mentioned polymerization solution F1 (containing components A and B) 48.
Instead of parts by weight, the D component was replaced by 54 parts by weight of Placcel 305 (manufactured by Daicel Chemical Industries), and the E component was replaced by 7.7 parts by weight of CI-2639 (manufactured by Nippon Soda). A curable composition was prepared. Then, using this composition, a cured film was obtained in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained cured film.

[0086]

[Table 1]

[0087]

INDUSTRIAL APPLICABILITY According to the present invention, a thermosetting composition (especially containing an oxetane ring) capable of forming a cured film (coating film) which has improved tackiness and retains adhesiveness to various substrates. A thermosetting composition comprising an oxetane compound such as a non-acrylic compound can be provided. That is, the cured film (coating film) obtained from the thermosetting composition of the present invention has improved tackiness, good adhesion to various substrates, and excellent transparency. .

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 133/16 C09D 133/16 163/00 163/00 167/00 167/00 167/04 167/04 171 / 00 171/00 171/02 171/02 // (C08L 71/02 C08L 33:14 33:14) F term (reference) 4J002 BG083 CD001 CD011 CD021 CD051 CH032 GH00 GH01 GH02 4J005 AA04 AA05 AA07 BB02 4J036 AA01 AB01 AB02 AB05 AB07 AB09 AB10 AD05 AD07 CA28 CD03 DB02 GA01 GA02 GA03 GA04 JA01 JA02 4J038 CG142 CH252 DB031 DB032 DB041 DB042 DB061 DB062 DB091 DB092 DB241 DB242 DB301 DB302 DD021 DD022 DD121 DD122 DF021 DF022 DF031 FA01 NA12 NA02 GA12 NA12 NA02 GA12 GA12 GA02 GA02 GA02 GA02 GA02 GA02 NA02

Claims (3)

[Claims] 1. An (A) oxetane ring-containing non-acrylic compound, (B) (meth) acrylic acid fluoroalkyl ester or polymer thereof, (C) oxirane ring-containing non-acrylic compound, (D) polyol compound, and ( E) A thermosetting composition comprising a thermal cationic polymerization initiator. 2. A (meth) acrylic acid fluoroalkyl ester or a (meth) acrylic acid ester fluoroalkyl ester constituting the polymer is an oxetane ring-containing (meth) acrylic acid ester or an oxirane ring-containing (meth) acrylic acid ester. The thermosetting composition according to claim 1, further comprising: 3. The thermosetting composition according to claim 1, wherein the polyol compound is a polylactone polyol, a polyester polyol, or a polyether polyol.