JPWO2006137260A1 - Polymerizable composition, ink composition, image forming method, ink jet recording apparatus, and alicyclic epoxide - Google Patents

Abstract

The present invention cures with high sensitivity even under high temperature conditions and has excellent storability, and the formed cured film is extremely excellent in adhesion, flexibility, storability, environmental resistance, especially durability against temperature changes. A polymerizable composition, a polymerization method of the polymerizable composition, an ink composition, an image forming method using the ink composition, an ink jet recording apparatus, and a specific alicyclic epoxy compound are provided.

Description

  The present invention relates to a polymerizable composition, which cures with high sensitivity even under high temperature conditions, has excellent storage stability, and the formed cured film has adhesion, flexibility, storage stability, environmental resistance, among others. The present invention relates to a polymerizable composition, an ink composition, an image forming method using the ink composition, an ink jet recording apparatus, and a specific alicyclic epoxide which are extremely excellent in durability against temperature changes.

  Conventionally, polymerizable compositions that are cured by active energy rays such as ultraviolet rays and electron beams or heat are various kinds of paints such as plastic, paper, woodwork and inorganic materials, adhesives, printing inks, printed circuit boards, and electrical insulation relations. Has been put to practical use. In recent years, printing inks, paints, adhesives and the like have been desired to further improve weather resistance and adhesion. In addition, as an inkjet ink system using these polymerized compositions, there is an ultraviolet curable ink jet ink that is cured by ultraviolet rays, and an inkjet method using this ultraviolet curable ink has a relatively low odor and is quick-drying. In recent years, attention has been paid to the fact that recording on a recording medium having no ink absorbability is possible, and ultraviolet curable ink-jet inks have been disclosed (for example, see Patent Documents 1 and 2). In this field, in addition to low viscosity, a film to be formed is required to be stronger and flexible. It has been disclosed that plasticity can be imparted by adding a plasticizer to ink-jet ink (see, for example, Patent Document 3). However, there is no description of ultraviolet curable ink-jet inks using melt-type inks and solvent-type inks.

  Further, when these inks are used, there is a problem that the curing sensitivity tends to vary depending on the type of recording material and the working environment.

  Inks using radically polymerizable compounds are subject to an oxygen inhibiting action, and therefore, when the amount of ink droplets is small, curing inhibition tends to occur. Ink using a cationically polymerizable compound (see, for example, Patent Documents 4 to 7) is not affected by oxygen, but has a problem that it is easily affected by moisture (humidity) at the molecular level.

Further, when the polymerizable composition is put into practical use for inkjet inks and the cured film is used as a product, the environment resistance of the cured film is required, but conventional epoxides such as Miasendioxide (CAS: 63869- 17-0) and a cured film prepared from a polymerizable composition using ATOFINA's terpinolene oxide and Daicel Chemical Industries' Celoxide 3000 have adhesion and flexibility when exposed to rapid temperature changes. There was a problem of significant reduction.
JP-A-6-200204 Special Table 2000-504778 JP-A-8-3493 JP 2001-220526 A JP 2002-188025 A JP 2002-317139 A JP 2003-55449 A

  The object of the present invention is to cure with high sensitivity even under high temperature conditions, excellent storage stability, and the formed cured film has extremely high adhesion, flexibility, storage stability, environmental resistance, especially durability against temperature changes. An excellent polymerizable composition, an ink composition, an image forming method using the ink composition, an ink jet recording apparatus, and a specific alicyclic epoxide (also referred to as an alicyclic alkylene oxide) are provided.

  The above object of the present invention has been achieved by the following constitution.

  1. A polymerizable composition comprising a compound having a molecular weight of 180 to 1000 represented by the following general formula (X).

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or an alkyl group, and R ³ is a saturation to which R ¹ and R ² in the general formula (X) are bonded. It is a substituent bonded at an arbitrary position of the hydrocarbon ring, and n is an integer from 0 to 7. When n is plural, R ³ may be the same as or different from each other. Is a (p + 1) -valent linking group or a simple bond bonded at any position to the saturated hydrocarbon ring to which R ¹ and R ² in general formula (X) are bonded, and p is 1 to 3 Q is an integer from 1 to 3. When p is plural, plural R ⁴ , R ⁵ and R ⁶ may be the same or different from each other, and plural q In this case, a plurality of L, R ⁴ , R ⁵ and R ⁶ may be the same or different from each other.)
2. ^2. The polymerizable composition as described in 1 above, wherein at least one of R ¹ and R ² is an alkyl group.

3. 3. The polymerizable composition as described in 1 or 2 above, wherein one of R ¹ and R ² is an alkyl group and the other is a hydrogen atom.

4). 4. The polymerizable composition as described in any one of 1 to 3 above, wherein one of R ¹ and R ² is an alkyl group having 1 to 3 carbon atoms, and the other is a hydrogen atom.

5. R < ⁵ > and R < ⁶ > is an alkyl group respectively, The polymerizable composition of any one of said 1-4 characterized by the above-mentioned.

  6). 6. The polymerizable composition as described in any one of 1 to 5 above, which comprises an acid generator.

  7. An ink composition comprising the polymerizable composition according to any one of 1 to 6 above.

  8. The ink composition as described in 7 above, wherein the viscosity at 25 ° C. is from 7 mPa · s to 40 mPa · s.

  9. 9. The ink composition as described in 7 or 8 above, which contains a pigment.

  10. An ink-jet recording head, wherein the ink composition according to any one of 7 to 9 is jetted onto a recording material in an image-like manner, and printing is performed on the recording material, the ink composition After the ink has landed, the ink composition is cured through a step of heating or a step of irradiating actinic rays for 0.001 seconds to 1.0 seconds.

  11. 11. The image forming method as described in 10 above, wherein the minimum ink droplet amount ejected from each nozzle of the ink jet recording head is 2 pl to 15 pl.

  12 12. An ink jet recording apparatus used in the image forming method according to 10 or 11, wherein the ink composition is ejected after the recording head is heated to 35 ° C. to 100 ° C.

  13. 12. An ink jet recording apparatus used in the image forming method according to 10 or 11, wherein the recording medium is heated to 35 ° C. to 60 ° C. when the ink composition is ejected.

  14 The compound characterized by the molecular weight represented by the following general formula (X-A) being 180-1000.

(Wherein R ¹¹ , R ¹² , R ¹⁵ and R ¹⁶ represent a hydrogen atom or an alkyl group, and R ¹³ represents an alkyl bonded to an arbitrary position of the saturated hydrocarbon ring in the general formula (X-A)). M represents an integer of 0 to 7, R ¹⁴ represents a hydrogen atom or an alkyl group, L ² is bonded to an arbitrary position of the saturated hydrocarbon ring in the general formula (X-A), An alkylene group, an oxygen atom, or a divalent linking group formed by a combination of the alkylene group and the oxygen atom.)
15. 15. The compound according to 14 above, wherein the general formula (X-A) is represented by the following general formula (X-B).

(Wherein R ²⁵ and R ²⁶ each represents an alkyl group, R ²⁴ represents a hydrogen atom or an alkyl group, and L ³ represents an alkylene group, an oxygen atom, or a combination of the alkylene group and the oxygen atom. Represents a divalent linking group to be formed.)

  According to the present invention, it is cured with high sensitivity even under high temperature conditions and has excellent storage stability, and further, the formed cured film has extremely excellent adhesion, flexibility, storage stability, environmental resistance, especially durability against temperature changes. The polymerizable composition, the ink composition, the image forming method using the ink composition, the ink jet recording apparatus, and the specific alicyclic epoxide can be provided.

It is a figure which shows the structure of the principal part of the recording device used for this invention. It is a figure which shows the structure of the principal part of another recording apparatus used for this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Recording device 2 Head carriage 3 Recording head 4 Irradiation means 5 Platen part 6 Guide member 7 Bellows structure P Recording material

  In the polymerizable composition of the present invention, the composition defined in any one of claims 1 to 6 is cured with high sensitivity even under high temperature conditions, and has excellent storage stability. The cured film thus formed was able to obtain a polymerizable composition having excellent adhesion, flexibility, storage stability, environmental resistance, particularly durability against temperature change. In addition, an ink composition containing the polymerizable composition, an image forming method using the ink composition, an ink jet recording apparatus, and the like were obtained together, and a specific alicyclic epoxide could be provided. .

<< Polymerizable composition >>
The polymerizable composition of the present invention will be described.

  As a result of intensive studies in view of the above problems, the present inventors have found that when using a polymerizable composition containing a compound having an epoxide structure (also referred to as an oxirane structure) represented by the general formula (X), It has been found that a cured film that is strong without being affected by environmental humidity even with a light source of illuminance, retains sufficient hardness and flexibility before and after storage for a long period of time, and has excellent resistance to temperature changes can be obtained. When the polymerizable composition is used as the ink composition and an image is formed, it has been found that a high-quality image can be obtained, and the present invention has been achieved.

<< Compound Represented by Formula (X) >>
The compound represented by the general formula (X) according to the present invention will be described.

R ¹ and R ² in the general formula (X) are hydrogen atoms or alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, iso-butyl group, sec-butyl group) Pentyl group, hexyl group, cyclopentyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, etc.), which may further have a substituent, Examples of the substituent of the alkyl group having a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkoxy group having 1 to 20 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl) Group, an acyloxy group having 1 to 20 carbon atoms (for example, an acetoxy group, a propionyloxy group, a trifluoroacetoxy group, etc.), an alkoxycarbonyl group having 1 to 20 carbon atoms (a methoxycarbonyl group, an ethoxycarbonyl group). , Tert-butoxycarbonyl group, etc.), C2-C20 alkylthiocarbonyl group (methylthiocarbonyl group, ethylthiocarbonyl group, tert-butylthiocarbonyl group, etc.), aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl Group, cyano group, nitro group, hydroxy group and the like. One of R ^{1 and} R ² is preferably an alkyl group, and the other is preferably a hydrogen atom. When R ¹ or R ² is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 3 carbon atoms. A group is more preferred, and a methyl group is most preferred.

R ³ in the general formula (X) represents a substituent. Examples of the substituent include the above-described alkyl group, halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), alkoxy having 1 to 20 carbon atoms. Group (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, etc.) An acyloxy group having 1 to 20 carbon atoms (for example, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), an alkoxycarbonyl group having 1 to 20 carbon atoms (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl) Group, etc.), an alkylthiocarbonyl group having 2 to 20 carbon atoms (methylthiocarbonyl group, ethylthiocarbo group) Group, tert-butylthiocarbonyl group, etc.), aryloxycarbonyl group, alkylsulfonyl group, aryl group, arylsulfonyl group, cyano group, nitro group, acylamino group, aryloxyamino group, amino group, ureido group, urethane Group, hydroxy group, and the like, and these substituents may be further substituted with the same substituents. As the substituent, an alkyl group, an alkoxy group, an acyloxy group, and an alkoxycarbonyl group are preferable.

N in the general formula (X) is an integer of 0 to 7. When n is plural, R ³ may be the same or different from each other.

R ^{4 to} R ⁶ in the general formula (X) each represent a hydrogen atom or an alkyl group, and examples of the alkyl group include the same groups as the alkyl group that can be R ¹ and R ² described above. As a combination of R ^{4 to} R ⁶ , R ⁴ is preferably a hydrogen atom, and R ⁵ and R ⁶ are preferably an alkyl group. When R ^{4 to} R ⁶ are alkyl groups, it is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 3 carbon atoms. It is more preferably an alkyl group, and most preferably a methyl group.

L in the general formula (X) is a (p + 1) -valent linking group or a simple bond, p is an integer from 1 to 3, q is an integer from 1 to 3, L is R ¹ and It is bonded to a saturated hydrocarbon ring containing R ² at an arbitrary position. q is preferably 1 or 2, and more preferably 1. Examples of the divalent linking group include —O— group, —S— group, —CO— group, —CS— group, —SO— group, —SO ₂ — group and the following groups, and these groups. The group which can be combined together can be mentioned.

Methylene group [—CH ₂ —]
Ethylidene group [> CHCH ₃ ]
Isopropylidene [> C (CH ₃ ) ₂ ]
1,2-ethylene group [—CH ₂ CH ₂ —]
1,2-propylene group [—CH (CH ₃ ) CH ₂ —]
1,3-propanediyl group [—CH ₂ CH ₂ CH ₂ —]
2,2-dimethyl-1,3-propanediyl group [—CH ₂ C (CH ₃ ) ₂ CH ₂ —]
2,2-dimethoxy-1,3-propanediyl group [—CH ₂ C (OCH ₃ ) ₂ CH ₂ —]
2,2-dimethoxymethyl-1,3-propanediyl group [—CH ₂ C (CH ₂ OCH ₃ ) ₂ CH ₂ —]
1-methyl-1,3-propanediyl group [—CH (CH ₃ ) CH ₂ CH ₂ —]
1,4-butanediyl group [—CH ₂ CH ₂ CH ₂ CH ₂ —]
1,5-pentanediyl group [—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —]
Oxydiethylene group [—CH ₂ CH ₂ OCH ₂ CH ₂ —]
Thiodiethylene group [—CH ₂ CH ₂ SCH ₂ CH ₂ —]
3-oxothiodiethylene group [—CH ₂ CH ₂ SOCH ₂ CH ₂ —]
3,3-dioxothiodiethylene group [—CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ —]
1,4-dimethyl-3-oxa-1,5-pentanediyl group [—CH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ —]
3-oxopentanediyl group [—CH ₂ CH ₂ COCH ₂ CH ₂ —]
1,5-dioxo-3-oxapentanediyl group [—COCH ₂ OCH ₂ CO—]
4-Oxa-1,7-heptanediyl group [—CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —]
3,6-dioxa-1,8-octanediyl group [—CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ —]
1,4,7-trimethyl-3,6-dioxa-1,8-octanediyl group [—CH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ —]
5,5-dimethyl-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (CH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —]
5,5-dimethoxy-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (OCH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —]
5,5-dimethoxymethyl-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (CH ₂ OCH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —]
4,7-dioxo-3,8-dioxa-1,10-decandiyl group [—CH ₂ CH ₂ O—COCH ₂ CH ₂ CO—OCH ₂ CH ₂ —]
3,8-dioxo-4,7-dioxa-1,10-decandiyl group [—CH ₂ CH ₂ CO—OCH ₂ CH ₂ O—COCH ₂ CH ₂ —]
1,3-cyclopentanediyl group [-1,3-C ₅ H ₈ —]
1,2-cyclohexanediyl group [-1,2-C ₆ H _10- ]
1,3-cyclohexanediyl group [-1,3-C ₆ H _10- ]
1,4-cyclohexanediyl group [-1,4-C ₆ H _10- ]
2,5-tetrahydrofurandiyl group [2,5-C ₄ H ₆ O—]
p- phenylene _{[-p-C 6 H 4 -} ]
m- phenylene group _{[-m-C 6 H 4 -} ]
α, α′-o-xylylene group [—o—CH ₂ —C ₆ H ₄ —CH ₂ —]
α, α'-m- xylylene group _{[-m-CH 2 -C 6 H} 4 -CH 2 -]
α, α′-p-xylylene group [-p-CH ₂ —C ₆ H ₄ —CH ₂ —]
Furan-2,5-diyl - bismethylene group _{[2,5-CH 2 -C 4 H} 2 O-CH 2 -]
Thiophene-2,5-diyl-bismethylene group [2,5-CH ₂ —C ₄ H ₂ S—CH ₂ —]
Isopropylidenebis -p- phenylene group _{[-p-C 6 H 4 -C} (CH 3) 2 -p-C 6 H 4 -]
When L is a trivalent or higher valent linking group, for example, a linking group in which a necessary number of hydrogen atoms are removed from the above divalent linking group is used as a bond.

L may have a substituent, examples of the substituent include the same groups as those described above for R ^3, and the linking group between the main chain and the substituent includes the above-described divalent linking group. Examples can be given.

  Preferred as a substituent on the linking group are an alkyl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, and a hydroxy group.

  Further, the substituent on the linking group may be a divalent or higher valent linking group by removing a necessary number of hydrogen atoms from any position to form a bond. In that case, any substituent in the general formula (X) may be used. The hydrogen atom bonded to the position may be removed and bonded at that position to form a ring, provided that the number of ring members is 3-5, more preferably 3-4. Most preferably.

  In particular, L is an oxirane formed by further adding at least one carbon atom in the chain as at least one carbon atom constituting the oxirane ring. The number of rings is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2.

L is preferably an oxygen atom or a divalent linking group having 1 to 8 carbon atoms in the main chain, which may contain an oxygen atom in the main chain, and may contain an oxygen atom or an oxygen atom in the main chain. A divalent linking group having 1 to 5 carbon atoms in a good main chain is more preferable. When p or q is plural, plural R ^{4 to} R ⁶ may be the same or different from each other. When q is plural, plural L may be the same or different from each other. .

  The molecular weight of the compound represented by the general formula (X) is preferably in the range of 180 to 1000, more preferably 200 to 700.

<< Compound Represented by Formula (X-A) >>
The compound represented by the different general formula (X-A) according to the present invention will be described.

  Of the compounds represented by the general formula (X), a compound represented by the general formula (X-A) is more preferable.

In the general formula (X-A), R ¹¹ , R ¹² , R ¹⁵ and R ¹⁶ each represent a hydrogen atom or an alkyl group, and R ¹³ represents any of the saturated hydrocarbon rings in the general formula (XA). Represents an alkyl group bonded to the position, m represents an integer of 0 to 7, R ¹⁴ represents a hydrogen atom or an alkyl group, and L ² represents a saturated hydrocarbon ring in the general formula (X-A). An alkylene group bonded to an arbitrary position (eg, methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, etc. Or a divalent linking group formed from an oxygen atom or a combination thereof.

One of R ¹¹ and R ¹² is preferably an alkyl group and the other is a hydrogen atom, and R ¹⁵ and R ¹⁶ are preferably an alkyl group. Suitable alkyl groups for R ¹¹ , R ¹² , R ¹³ , R ¹⁵ and R ¹⁶ are the same as the alkyl groups mentioned as examples of R ¹ and R ² above, preferably alkyl having 1 to 8 carbon atoms. Group, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group or an ethyl group. As for m, 0-5 are more preferable, and 0-3 are more preferable. When m is plural, plural R ¹³ may be the same or different. When R ¹⁴ is an alkyl group, preferred alkyl groups have the same meanings as preferred alkyl groups for R ¹¹ , R ¹¹ , R ¹³ , R ¹⁵ , and R ¹⁶ , but R ¹⁴ is most preferably a hydrogen atom. The alkylene group of L ^2, preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms. This alkylene group may be substituted with a substituent having the same meaning as the above-mentioned examples of the substituent of L, and the substituent may be further substituted with a substituent having the same meaning as the above-mentioned examples of the substituent of L. . Preferred as a substituent for the alkylene group of L ² is an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a hydroxy group, or a substituent in which these are substituted with a halogen atom. L ² may have an ether bond by containing an oxygen atom in the main chain of the alkylene group or in the substituent.

If the oxygen atoms contained in L ^2, the number of oxygen atoms is 1 to 5 preferably contained in L ^2, 1 to 3 is more preferable.

<< Compound Represented by Formula (X-B) >>
The compound represented by the general formula (X-B) according to the present invention will be described.

  Among the compounds represented by the general formula (X-A), a compound represented by the general formula (X-B) is particularly preferable.

In the general formula (X-B), R ²⁵ and R ²⁶ represent an alkyl group, R ²⁴ represents a hydrogen atom or an alkyl group, L ³ represents an alkylene group, an oxygen atom, or a combination thereof. Represents.

The alkyl group suitable for R ²⁵ and R ²⁶ has the same meaning as the alkyl group exemplified as the examples of R ¹ and R ² described above, preferably an alkyl group having 1 to 8 carbon atoms, more preferably a carbon number. 1 to 3 alkyl groups, particularly preferably a methyl group or an ethyl group. When R ²⁴ is an alkyl group, preferred alkyl groups have the same meanings as preferred alkyl groups for R ²⁵ and R ²⁶ , but R ²⁴ is most preferably a hydrogen atom. The alkylene group of L ^3, preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms. This alkylene group may be substituted with a substituent having the same meaning as in the above-described examples of the substituent for L, and the substituent may be further substituted with a substituent having the same meaning. As the substituent for the alkylene group of L ³ , an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a hydroxy group, or a substituent in which these are substituted with a halogen atom is preferable. L ³ may have an ether bond by containing an oxygen atom in the main chain of the alkylene group or in the substituent.

If the oxygen atoms contained in the L ^3, the number of oxygen atoms is 1 to 5 preferably contained in the L ^3, 1 to 3 is more preferred.

  Although the specific example of a compound represented by general formula (X) below is shown, this invention is not limited to these.

  The compound represented by the general formula (X) is not limited in its production method. Org. Chem. 33, 1656 (1968). J. et al. Org. Chem. 42, 1197 (1977). J. et al. Org. Chem. 62, 3748 (1997). Tetrahedron Lett. 29, 4177 (1988). Maruzen KK Publishing, 4th edition Experimental Chemistry Course 20 Organic Synthesis II, 213, 1992, Ed. By Alfred Hasfner, The Chemistry of Heterocyclic compounds, Vol. 30, Advertisement, Small Ring Heterocycle part3 Oxilanes, John & Wiley and Sons, An Inc. No. 5, 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, Japanese Patent Laid-Open No. 11-100308, Japanese Patent Laid-Open No. 4-36263, Japanese Patent Laid-Open No. 4-69360, etc. Can be synthesized.

  Hereinafter, although the synthesis example of the compound represented by general formula (X) which concerns on this invention is shown, this invention is not limited to these.

<< Synthesis Example 1: Synthesis of X-2 >>
The reactor was charged with 11.8 g of bisabolol and 120 ml of methylene chloride and stirred. Next, a solution prepared by dissolving 36 g of m-chloroperbenzoic acid (mCPBA) in 360 ml of methylene chloride was added dropwise to the stirring methylene chloride solution of bisabolol at room temperature over 1 hour. After further stirring for 2 hours, 100 ml of saturated sodium sulfite aqueous solution was added to inactivate the remaining excess mCPBA, the organic layer was separated using a separatory funnel, and the organic substance was extracted from the aqueous layer with 100 ml of methylene chloride. did. The organic layers were mixed and washed twice with 100 ml of saturated sodium bicarbonate aqueous solution, and then washed successively with 100 ml of pure water and 100 ml of saturated saline. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated, and then the mixture was separated by silica gel chromatography to obtain 9 g of X-2. ^The target product was confirmed by ¹ H-NMR and mass spectrum (parent peak 255).

¹ H-NMR (CDCl ₃ ) δ (ppm):
1.0-2.2 (m, 24H, methyl, methylene, cyclohexane ring methylene, methine, hydroxy group), 2.9-3.1 (m, 1H, epoxy root), 3.6-3.8 ( m, 1H, epoxy root)
<< Synthesis Example 2: Synthesis of X-4 >>
The reactor was charged with 12 g of the following intermediate A and 90 ml of methylene chloride. Next, a solution prepared by dissolving 26.3 g of m-chloroperbenzoic acid (mCPBA) in 270 ml of methylene chloride was dropped into the stirring methylene chloride solution of intermediate A over 1 hour at room temperature. After further stirring for 2 hours, 80 ml of saturated sodium sulfite aqueous solution was added to inactivate the remaining excess mCPBA, the organic layer was separated using a separatory funnel, and the organic substance was extracted from the aqueous layer with 80 ml of methylene chloride. did. The organic layers were mixed and washed twice with 80 ml of saturated sodium bicarbonate aqueous solution, and then washed sequentially with 80 ml of pure water and 80 ml of saturated saline. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated, and then the mixture was separated by silica gel chromatography to obtain 12 g of X-4. ^The target product was confirmed by ¹ H-NMR and mass spectrum (parent peak 297).

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.2-2.2 (m, 26H, methyl, methylene, cyclohexane ring methylene, methine, hydroxy group), 2.6-2.8 (m, 1H) , Epoxy root), 2.9-3.2 (m, 1H, epoxy root)

<< Synthesis Example 3: Synthesis of X-6 >>
The reactor was charged with 6.6 g of the following intermediate B and 40 ml of methylene chloride. Next, a solution prepared by dissolving 11 g of m-chloroperbenzoic acid (mCPBA) in 120 ml of methylene chloride was added dropwise to the stirring solution of Intermediate B in methylene chloride at room temperature over 1 hour. After further stirring for 2 hours, 40 ml of saturated sodium sulfite aqueous solution was added to quench the remaining excess mCPBA, the organic layer was separated using a separatory funnel, and the organic substance was extracted from the aqueous layer with 40 ml of methylene chloride. did. The organic layers were mixed, washed twice with 40 ml saturated aqueous sodium bicarbonate solution, and then washed successively with 40 ml pure water and 40 ml saturated brine. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated, and then the mixture was separated by silica gel chromatography to obtain 4.5 g of X-6. ^The target product was confirmed by ¹ H-NMR and mass spectrum (parent peak 351).

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.1-2.2 (m, 23H, methyl, methylene, cyclohexane ring methylene, methine, hydroxy group), 2.6-2.8 (m, 1H) , Epoxy root), 2.9-3.2 (m, 1H, epoxy root)

<< Synthesis Example 4: Synthesis of X-5 >>
13 g of the following intermediate C and 80 ml of methylene chloride were placed in the reactor and stirred. Next, a solution prepared by dissolving 22 g of m-chloroperbenzoic acid (mCPBA) in 240 ml of methylene chloride was dropped into the stirring methylene chloride solution of Intermediate C over 1 hour at room temperature. After further stirring for 2 hours, 80 ml of saturated sodium sulfite aqueous solution was added to inactivate the remaining excess mCPBA, the organic layer was separated using a separatory funnel, and the organic substance was extracted from the aqueous layer with 80 ml of methylene chloride. did. The organic layers were mixed and washed twice with 80 ml of saturated sodium bicarbonate aqueous solution, and then washed sequentially with 80 ml of pure water and 80 ml of saturated saline. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated, and then the mixture was separated by silica gel chromatography to obtain 10 g of X-5. ^The target product was confirmed by ¹ H-NMR and mass spectrum (parent peak 283).

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.2-2.2 (m, 26H, methyl, methylene, cyclohexane ring methylene, methine, hydroxy group), 2.6-2.8 (m, 1H) , Epoxy root), 2.9-3.2 (m, 1H, epoxy root), 3.2-3.4 (m, 2H, ethoxy group methylene)

<< Synthesis Examples 5-7 >>
As shown in the following formula, X-21, X-28 and X-39 were obtained by the same method as in Synthesis Examples 1 to 4 described above. The structure was confirmed by ¹ H-NMR and mass spectrum (respective parent peaks were 227, 241 and 325).

  In the polymerizable composition of the present invention, a compound having an oxetane ring can be used in combination with the compound represented by the general formula (X). Examples of the compound having an oxetane ring include JP-A-2001-220526, Any known oxetane compound described in JP-A-2001-310937 can be used.

  In the polymerizable composition of the present invention, the 2-position of the oxetane ring is not substituted with the compound represented by the general formula (X) in order to obtain high curability of the composition and desired physical properties of the cured film. It is preferable to use an oxetane compound in combination.

  As an example of the oxetane compound in which the 2-position is not substituted, a compound represented by the general formula (101) described in paragraph No. 0091 (chemical formula 16) of JP-A No. 2004-143135 can be mentioned.

  In the polymerizable composition of the present invention, it is preferable to use an oxetane compound containing only one oxetane ring in combination in order to obtain appropriate handling ease of the composition due to the viscosity and storage stability of the composition. Examples include Aron Oxetane OXT-101 (Exemplary Compound 1) and OXT-212 (Exemplary Compound 2) manufactured by Toagosei Co., Ltd.

  Furthermore, as an oxetane compound that can be preferably used in the present invention, a compound having two oxetane rings is particularly preferred because the resulting composition has excellent tackiness, low viscosity and excellent workability. An example of a compound having two oxetane rings includes a compound represented by the general formula (102) described in paragraph No. 0094 (Chemical Formula 17) of JP-A-2004-143135.

  Specific examples of the compound having two oxetane rings include Exemplified Compounds 41 and 42 described in paragraph No. 0106 (Chemical Formula 22) of JP-A No. 2004-143135.

  Among the compounds having two oxetane rings, preferable examples other than the above-described compounds include compounds represented by general formula (107) described in paragraph No. 0109 (Chemical Formula 23) of JP-A No. 2004-143135. is there.

  An example of a compound having 3 to 4 oxetane rings is a compound represented by the general formula (108) described in paragraph No. 0111 (Chemical Formula 24) of JP-A No. 2004-143135.

  As an example of a compound having 3 to 4 oxetane rings, Exemplified Compound 43 described in paragraph No. 0116 (Chemical Formula 26) of JP-A No. 2004-143135 can be mentioned.

  Furthermore, examples of the compound having 1 to 4 oxetane rings other than those described above are represented by the general formula (109) described in paragraph No. 0118 (Chemical Formula 27) of JP-A No. 2004-143135. Compounds.

  Preferable specific examples of the oxetane compound used in the present invention include exemplified compounds 44 to 46 described in paragraph No. 0121 (Chemical Formula 28) of JP-A No. 2004-143135.

  The production method of each compound having an oxetane ring described above is not particularly limited, and may be a conventionally known method. For example, Pattison (DB Pattison, J. Am. Chem. Soc., 3455, 79 ( 1957)) discloses a method for synthesizing an oxetane ring from a diol. In addition to these, compounds having 1 to 4 oxetane rings having a high molecular weight of about 1000 to 5000 are also included. Specific examples of these compounds include compounds described in paragraph No. 0123 (Chemical 29) of JP-A No. 2004-143135.

  In the polymerizable composition of the present invention, together with the compound represented by the general formula (X), an alicyclic epoxide represented by the following general formula (A) (also referred to herein as an alicyclic epoxide) It is preferable to use these in combination when it is necessary to impart desired physical properties such as flexibility to the cured film.

In the formula, R ₁₀₁ represents a substituent not containing a cationic polymerizable or radical polymerizable reactive functional group, and m10 represents 1, 2, 3 or 4.

In the general formula (A), R ₁₀₁ represents a substituent that does not contain a cationic polymerizable or radical polymerizable reactive functional group. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom). Atoms), alkyl groups having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.), cycloalkyl groups having 3 to 6 carbon atoms (for example, cyclopropyl group, Cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.), C1-C20 alkoxy group (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.) , An acyl group having 2 to 20 carbon atoms (for example, an acetyl group, a propionyl group, a trifluoroacetyl group, etc.), an acyloxy group having 2 to 20 carbon atoms ( For example, an acetoxy group, a propionyloxy group, a trifluoroacetoxy group, etc.), an acylthio group having 2 to 20 carbon atoms (for example, an acetylthio group, a propionylthio group, a trifluoroacetylthio group, etc.), an alkoxycarbonyl having 2 to 20 carbon atoms. Groups (for example, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), C2-C20 alkylthiocarbonyl groups (for example, methylthiocarbonyl group, ethylthiocarbonyl group, tert-butylthiocarbonyl group, etc.), etc. Is mentioned.

  These groups may further have a substituent. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkoxy group having 1 to 20 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n -Butoxy group, tert-butoxy group, etc.), C2-C20 acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, etc.), C2-C20 acyloxy group (for example, acetoxy group, propionyl) Oxy group, trifluoroacetoxy group, etc.), C2-C20 alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.), C2-C20 alkylthiocarbonyl group (for example, Methylthiocarbonyl group, ethylthiocarbonyl group, tert-butylthiocar Sulfonyl group), an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a cyano group, and nitro group go up. As the substituent, a halogen atom, an alkoxy group, an acyloxy group, and an alkoxycarbonyl group are preferable.

  A more preferred alicyclic epoxide is a compound represented by the following general formula (AI) from the viewpoint of producing a cured film having a high hardness and further improving the substrate adhesion of the cured film.

In the formula, R ₁₁₁ represents a substituent, and m11 represents 0, 1, 2, or 3. R ₁₁₂ , R ₁₁₃ and R ₁₁₄ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. Y ₁₁ and Y ₁₂ each independently represent O or S, p11 represents 0, 1 or 2, q11 represents 0 or 1, r11 represents 0 or 1, and s11 represents 0 or 1.

In the general formula (AI), examples of the substituent represented by R ₁₁₁ include a halogen atom (eg, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 20 carbon atoms (eg, a methyl group). , Ethyl group, propyl group, isopropyl group, butyl group, etc.), C1-C20 alkoxy group (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert- Butoxy group etc.), acyl group (eg acetyl group, propionyl group, trifluoroacetyl group etc.), acyloxy group having 1 to 20 carbon atoms (eg acetoxy group, propionyloxy group, trifluoroacetoxy group etc.), carbon Several to 20 alkoxycarbonyl groups (for example, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group) Etc.), an alkylthiocarbonyl group having 2 to 20 carbon atoms (eg, methylthiocarbonyl group, ethylthiocarbonyl group, tert-butylthiocarbonyl group, etc.), aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, cyano group, nitro Groups and the like. As the substituent, an alkyl group, an alkoxy group, and an alkoxycarbonyl group are preferable.

R ₁₁₂ , R ₁₁₃ and R ₁₁₄ represent a hydrogen atom or a substituted or unsubstituted alkyl group. As an example of an alkyl group, the same group as the example of the alkyl group of _R111 mentioned above can be mentioned. Examples of the substituent of the alkyl group having a substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkoxy group having 1 to 20 carbon atoms (for example, methoxy group, ethoxy group, n- Propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (for example, acetyl group, propionyl group, trifluoroacetyl group, etc.), acyloxy group having 1 to 20 carbon atoms (for example, An acetoxy group, a propionyloxy group, a trifluoroacetoxy group, etc.), an alkoxycarbonyl group having 1 to 20 carbon atoms (for example, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, etc.), an alkylthio having 2 to 20 carbon atoms. A carbonyl group (eg, methylthiocarbonyl group, ethylthiocarbonyl group, ter - butyl thiocarbonyl group), an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a cyano group, a nitro group and the like, Preferable substituents are an alkoxy group, an alkoxycarbonyl group.

Y ₁₁ and Y ₁₂ represent O or S, and O is preferable. m11 represents 0 to 3 and is preferably 1 or 2. p11 represents 0, 1 or 2, and q11, r11 and s11 represent 0 or 1.

  A particularly preferred alicyclic epoxide is a compound represented by the following general formula (A-II) in that a cured film having a high hardness is formed and the adhesion of the cured film to the substrate is improved.

In the formula, R ₁₂₁ represents a substituent, and m12 represents 0, 1 or 2. R ₁₂₂ , R ₁₂₃ and R ₁₂₄ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. Y ₂₁ and Y ₂₂ each independently represent O or S, p12 represents 0, 1 or 2, q12 represents 0 or 1, r12 represents 0 or 1, and s12 represents 0 or 1.

In the above formula, R ₁₂₁ has the same meaning as R ₁₁₁ . Y ₂₁ and Y ₂₂ represent O or S, and O is preferred. m12 represents 0 to 2, and 0 or 1 is preferable. p12 represents 0, 1 or 2, and q12, r12 and s12 represent 0 or 1. R ₁₂₂ , R ₁₂₃ , and R ₁₂₄ are synonymous with R ₁₁₂ , R ₁₁₃ , and R ₁₁₄ .

  More preferred alicyclic epoxides are those having the following general formulas (A-III) and general ones in that they have high curing sensitivity, improve the adhesion of the cured film to the substrate, and are less susceptible to curing sensitivity due to fluctuations in the printing environment. It is a compound represented by the formula (A-IV) or the general formula (A-V).

In the formula, R ₁₃₁ represents a substituent, and m13 represents 0, 1 or 2. R ₁₃₂ , R ₁₃₃ and R ₁₃₄ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. p13 represents 0, 1 or 2, and q13 represents 0 or 1.

In the formula, R ₁₄₁ represents a substituent, and m14 represents 0, 1 or 2. R ₁₄₂ , R ₁₄₃ and R ₁₄₄ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. p14 represents 0, 1 or 2.

In the formula, R ₁₅₁ represents a substituent, and m15 represents 0, 1 or 2. R ₁₅₄ represents a hydrogen atom or a substituted or unsubstituted alkyl group. s15 represents 0 or 1.

In the above formula, R ₁₃₁ , R ₁₄₁ and R ₁₅₁ are as defined above for R ₁₁₁ . m13, m14 and m15 represent 0 to 2, and 0 or 1 is preferable. p13 and p14 represent 0, 1 or 2, and q13 and s15 represent 0 or 1. R ₁₃₂ , R ₁₃₃ , R ₁₃₄ , R ₁₄₂ , R ₁₄₃ , R ₁₄₄ , and R ₁₅₄ are synonymous with R ₁₁₂ , R ₁₁₃ , and R ₁₁₄ .

  A particularly preferred alicyclic epoxide is represented by the following general formula (A-VI) in that it has high curing sensitivity, improves the adhesion of the cured film to the substrate, and is less susceptible to curing sensitivity due to fluctuations in the printing environment. It is a compound.

In the above formula, R ₁₆₁₁ and R ₁₆₁₂ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, t-butyl group). , A pentyl group, a hexyl group, and the like, and an alkyl group is preferably a methyl group, an ethyl group or a propyl group. R ₁₆₂ , R ₁₆₃ and R ₁₆₄ have the same _meanings as R ₁₁₂ , R ₁₁₃ and R ₁₁₄ . q16 represents 0 or 1.

  Hereinafter, although the specific example of the alicyclic epoxide represented by General formula (A) which can be used for this invention is shown, this invention is not limited to these.

Although there is no restriction | limiting in particular in content of the compound represented by general formula (X) in the polymeric composition of this invention, It is preferable that it is the range of 0.1 mass% to 60 mass%.

  In the polymerizable composition of the present invention, a polyfunctional alicyclic epoxide may be used in combination with the compound represented by the general formula (X), the oxetane compound and the monofunctional epoxide represented by the general formula (A). it can. Thereby, a further effect of improving the sensitivity or an effect of improving the properties of the cured film can be obtained.

  Preferred as the bifunctional alicyclic epoxide is a polyfunctional epoxide represented by the following general formula (B).

In the formula, R ₂₀₁ and R ₂₀₂ each represent a substituent, and m20 and n20 each represent 0, 1 or 2, and 0 or 1 is preferable. r0 represents 1-3. L ₀ represents an r0 + 1-valent linking group or a single bond having 1 to 15 carbon atoms, which may contain an oxygen atom or a sulfur atom in the main chain.

In the above formula, examples of the substituent represented by R ₂₀₁ and R ₂₀₂ include a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, Ethyl group, propyl group, isopropyl group, butyl group, etc.), C1-C6 alkoxy group (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group) Group), acyl group (eg acetyl group, propionyl group, trifluoroacetyl group etc.), acyloxy group (eg acetoxy group, propionyloxy group, trifluoroacetoxy group etc.), alkoxycarbonyl group (eg methoxycarbonyl group) Ethoxycarbonyl group, tert-butoxycarbonyl group and the like. As the substituent, an alkyl group, an alkoxy group, and an alkoxycarbonyl group are preferable.

Examples of the divalent linking group having 1 to 15 carbon atoms that may contain an oxygen atom or a sulfur atom in the main chain represented by L ₀ include the following groups, and these groups and —O— group, —S— group, Examples include groups formed by combining a plurality of —CO— groups and —CS— groups.

Methylene group [—CH ₂ —]
Ethylidene group [> CHCH ₃ ]
Isopropylidene [> C (CH ₃ ) ₂ ]
1,2-ethylene group [—CH ₂ CH ₂ —]
1,2-propylene group [—CH (CH ₃ ) CH ₂ —]
1,3-propanediyl group [—CH ₂ CH ₂ CH ₂ —]
2,2-dimethyl-1,3-propanediyl group [—CH ₂ C (CH ₃ ) ₂ CH ₂ —]
2,2-dimethoxy-1,3-propanediyl group [—CH ₂ C (OCH ₃ ) ₂ CH ₂ —]
2,2-dimethoxymethyl-1,3-propanediyl group [—CH ₂ C (CH ₂ OCH ₃ ) ₂ CH ₂ —]
1-methyl-1,3-propanediyl group [—CH (CH ₃ ) CH ₂ CH ₂ —]
1,4-butanediyl group [—CH ₂ CH ₂ CH ₂ CH ₂ —]
1,5-pentanediyl group [—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —]
Oxydiethylene group [—CH ₂ CH ₂ OCH ₂ CH ₂ —]
Thiodiethylene group [—CH ₂ CH ₂ SCH ₂ CH ₂ —]
3-oxothiodiethylene group [—CH ₂ CH ₂ SOCH ₂ CH ₂ —]
3,3-dioxothiodiethylene group [—CH ₂ CH ₂ SO ₂ CH ₂ CH ₂ —]
1,4-dimethyl-3-oxa-1,5-pentanediyl group [—CH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ —]
3-oxopentanediyl group [—CH ₂ CH ₂ COCH ₂ CH ₂ —]
1,5-dioxo-3-oxapentanediyl group [—COCH ₂ OCH ₂ CO—]
4-Oxa-1,7-heptanediyl group [—CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —]
3,6-dioxa-1,8-octanediyl group [—CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ —]
1,4,7-trimethyl-3,6-dioxa-1,8-octanediyl group [—CH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ —]
5,5-dimethyl-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (CH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —]
5,5-dimethoxy-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (OCH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —]
5,5-dimethoxymethyl-3,7-dioxa-1,9-nonanediyl group [—CH ₂ CH ₂ OCH ₂ C (CH ₂ OCH ₃ ) ₂ CH ₂ OCH ₂ CH ₂ —]
4,7-dioxo-3,8-dioxa-1,10-decandiyl group [—CH ₂ CH ₂ O—COCH ₂ CH ₂ CO—OCH ₂ CH ₂ —]
3,8-dioxo-4,7-dioxa-1,10-decandiyl group [—CH ₂ CH ₂ CO—OCH ₂ CH ₂ O—COCH ₂ CH ₂ —]
1,3-cyclopentanediyl group [-1,3-C ₅ H ₈ —]
1,2-cyclohexanediyl group [-1,2-C ₆ H _10- ]
1,3-cyclohexanediyl group [-1,3-C ₆ H _10- ]
1,4-cyclohexanediyl group [-1,4-C ₆ H _10- ]
2,5-tetrahydrofurandiyl group [2,5-C ₄ H ₆ O—]
p- phenylene _{[-p-C 6 H 4 -} ]
m- phenylene group _{[-m-C 6 H 4 -} ]
α, α′-o-xylylene group [—o—CH ₂ —C ₆ H ₄ —CH ₂ —]
α, α'-m- xylylene group _{[-m-CH 2 -C 6 H} 4 -CH 2 -]
α, α'-p- xylylene group _{[-p-CH 2 -C 6 H} 4 -CH 2 -]
Furan-2,5-diyl - bismethylene group _{[2,5-CH 2 -C 4 H} 2 O-CH 2 -]
Thiophene-2,5-diyl-bismethylene group [2,5-CH ₂ —C ₄ H ₂ S—CH ₂ —]
Isopropylidenebis -p- phenylene group _{[-p-C 6 H 4 -C} (CH 3) 2 -p-C 6 H 4 -]
Examples of the trivalent or higher linking group include a group formed by removing a hydrogen atom at an arbitrary site from the divalent linking group described above as much as necessary, and an —O— group, —S— group, —CO—. And a group formed by combining a plurality of groups and -CS- groups.

L ₀ may have a substituent. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.) ), An alkoxy group having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group, etc.), acyl group (for example, acetyl group, Propionyl group, trifluoroacetyl group, etc.), acyloxy group (eg, acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, etc.) ) And the like. As the substituent, an alkyl group, an alkoxy group, and an alkoxycarbonyl group are preferable.

L ₀ is preferably a divalent linking group having 1 to 8 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain, and more preferably a divalent linking group having 1 to 5 carbon atoms in which the main chain is composed solely of carbon. preferable.

  Particularly preferred alicyclic epoxides are those represented by the following general formula (B-I) or (B-II) in terms of producing a cured film having high hardness and further improving the adhesion of the cured film to the substrate. A compound.

In the formula, R ₂₁₁ and R ₂₁₂ represent substituents, m21 and n21 represent 0, 1 or 2, and 0 or 1 is preferred. p1 and q1 each represents 0 or 1. r1 represents 1-3. L ₁ represents a C 1-15 r 1 + 1 valent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain.

In the formula, R ₂₂₁ and R ₂₂₂ represent a substituent, m22 and n22 represent 0, 1 or 2, and 0 or 1 is preferable. p2 and q2 each represents 0 or 1. r2 represents 1-3. L ₂ represents an r2 + 1-valent linking group or a single bond having 1 to 15 carbon atoms which may contain an oxygen atom or a sulfur atom in the main chain.

In the above formula, R ₂₁₁ , R ₂₁₂ , R ₂₂₁ and R ₂₂₂ have the same meaning as R ₁₁₁ in the general formula (A-1).

Examples of the divalent linking group having 1 to 15 carbon atoms that may contain an oxygen atom or a sulfur atom in the main chain represented by L ₁ and L ₂ are the same as those described in the description of L ₀ . L ₁ and L ₂ are preferably a C 1-8 divalent linking group that may contain an oxygen atom or a sulfur atom in the main chain, and the C 1-5 divalent linking group in which the main chain consists only of carbon. Groups are more preferred.

  A particularly preferred alicyclic epoxide is a compound represented by the following general formula (B-III) or (B-IV) in that the curing sensitivity is high and the curing sensitivity is not easily affected by fluctuations in the printing environment. is there.

In the formula, R ₂₃₁ and R ₂₃₂ represent a substituent, and m23 and n23 represent 0 or 1. p3 and q3 each represents 0 or 1. r3 represents 1-3. L ₃ represents a C 1-15 r 3 + 1 valent linking group or single bond that may contain an oxygen atom or a sulfur atom in the main chain.

In the formula, R ₂₄₁ and R ₂₄₂ represent substituents, and m24 and n24 represent 0 or 1. p4 and q4 each represents 0 or 1. r4 represents 1-3. L ₄ represents an r4 + 1-valent linking group or a single bond having 1 to 15 carbon atoms, which may contain an oxygen atom or a sulfur atom in the main chain.

In the above formula, R ₂₃₁ , R ₂₃₂ , R ₂₄₁ and R ₂₄₂ have the same _{meaning as} R ₁₁₁ in the general formula (A-1). Examples of the divalent linking group having 1 to 15 carbon atoms that may contain an oxygen atom or a sulfur atom in the main chain represented by L ₃ and L ₄ are the same as those described in the description of L ₀ .

  Although the specific example of a preferable alicyclic epoxide is shown below, this invention is not limited to these.

  As the addition amount of these epoxides, from the viewpoint of improving the stability of curability by the curing environment (temperature, humidity) and keeping the film physical properties after curing appropriate, the addition amount is 10 mass% to 40 mass%. Preferably, it is in the range of 20% by mass to 40% by mass.

  In the present invention, one type of polyfunctional epoxide may be used alone, or two or more types may be used in appropriate combination.

  These alicyclic epoxides can be produced by any method. For example, Maruzen KK Publishing, 4th Edition, Experimental Chemistry Course 20 Organic Synthesis II, 213, 1992, Ed. By Alfred Hasfner, The Chemistry of Heterocyclic compounds, Vol. 30, Advertisement, Small Ring Heterocycle part3 Oxilanes, John & Wiley and Sons, An Inc. No. 5, 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, JP-A-11-100308, JP-A-4-36263, JP-A-4-69360, etc. Can be synthesized.

  A conventionally known polymerization initiator can be used for the polymerizable composition of the present invention, and the polymerization initiator is preferably an acid generator, and when used as an ink composition, it is preferably a photoacid generator. . By using a polymerization initiator, the polymerizable composition of the present invention can be polymerized by adding actinic rays or heat, or both. However, the polymerizable composition of the present invention can be polymerized with an ink composition (ink composition). Is described in detail later.), The polymer is preferably polymerized by irradiation with actinic rays, and more preferably polymerized by irradiation with ultraviolet rays.

  As the photoacid generator used in the cationic polymerization type ink using the polymerizable composition of the present invention, for example, a chemical amplification type photoresist or a compound used for photocationic polymerization is used (edited by Organic Electronics Materials Research Group, "Organic materials for imaging", Bunshin Publishing (1993), pages 187-192). Examples of compounds suitable for the present invention are listed below.

First, B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , p-CH ₃ C ₆ H ₄ of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium and phosphonium. SO ₃ ^- salt, CF ₃ SO ₃ ^- and sulfonic acid salts such as salts. Those having a borate compound as a counter anion and PF ₆ ^- salt acid generation capability higher preferred. Specific examples of the onium compound include compounds described in JP-A No. 2004-143135, paragraph No. 0149 (Chemical Formula 31).

  Secondly, sulfonated substances that generate sulfonic acid can be mentioned, and specific examples include compounds described in JP-A No. 2004-143135 and paragraph No. 0151 (Chemical Formula 32).

  Thirdly, a halide that generates hydrogen halide can also be used, and specific examples thereof include compounds described in JP-A No. 2004-143135 and paragraph No. 0152 (Chemical Formula 33). .

  Fourthly, an iron allene complex can be mentioned, and specific examples include compounds described in JP-A No. 2004-143135, paragraph No. 0155 (Chemical Formula 34).

  Examples of the photocationic polymerization initiator used in the present invention include arylsulfonium salt derivatives (for example, Cyracure UVI-6990, Cyracure UVI-6974, manufactured by Union Carbide, Adekaoptomer SP-150, manufactured by Asahi Denka Kogyo Co., Ltd., and Adeka). Optomer SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172), allyl iodonium salt derivatives (for example, RP-2074 manufactured by Rhodia), allene-ion complex derivatives (for example, Irgacure manufactured by Ciba Geigy) 261), acid generators such as diazonium salt derivatives, triazine-based initiators and other halides. It is preferable to contain a cationic polymerization initiator in the ratio of 0.2 mass part-20 mass parts from a viewpoint of sclerosis | hardenability improvement with respect to 100 mass parts of compounds which have cationic polymerizability.

  Preferable photoacid generators used in the present invention are onium salts such as sulfonium salts, iodonium salts, ammonium salts, phosphonium salts, etc. Among them, sulfonium salt compounds are preferable. More preferred sulfonium salt compounds include sulfonium salts represented by general formulas (I-1), (I-2) and (I-3) described in claim 8 of JP-A No. 2004-143135. be able to.

  Further, a more detailed description of the sulfonium salts represented by the general formulas (I-1), (I-2), and (I-3) is described in paragraph numbers 0159 to 0171 of JP-A-2004-143135. ing.

  Specific examples of the sulfonium salts represented by the general formulas (I-1), (I-2) and (I-3) are described in paragraph numbers 0174 to 0178 (Chemical Formulas 35 to 39) of JP-A No. 2004-143135. PI-1 to PI-37 can be mentioned.

  In addition to the constituent elements described above, various additives can be used in the polymerizable composition of the present invention.

  Examples of the additive that can be used in the polymerizable composition of the present invention include a photopolymerization accelerator.

  Examples of the photopolymerization accelerator include anthracene, anthracene derivatives (for example, Adekaoptomer SP-100 manufactured by Asahi Denka Kogyo Co., Ltd.), phenothiazine (10H-phenothiazine), and phenothiazine derivatives (for example, 10-methylphenothiazine, 10-ethylphenothiazine). 10-decylphenothiazine, 10-acetylphenothiazine, 10-decylphenothiazine-5-oxide, 10-decylphenothiazine-5,5-dioxide, 10-acetylphenothiazine-5,5-dioxide, etc.). These photopolymerization accelerators can be used alone or in combination.

  When the polymerizable composition of the present invention is used as a curable composition for forming a cured film, the viscosity is preferably 0.1 mPa · s to 1000 mPa · s, and preferably 0.1 mPa · s to 500 mPa · s. More preferably, it is more preferably 0.1 mPa · s to 300 mPa · s, and most preferably 0.1 mPa · s to 150 mPa · s.

<Ink composition>
The ink composition (also simply referred to as ink) of the present invention will be described.
The ink composition of the present invention refers to a composition containing the polymerizable composition of the present invention and a coloring material, and may contain other various additives.

  As the color material used in the ink composition using the polymerizable composition of the present invention, any color material that can be dissolved or dispersed in the main component of the polymerizable compound can be used without limitation, and an oil-soluble dye or pigment is preferable. Pigments are preferred from the standpoints of properties and light resistance.

  The pigments that can be preferably used in the present invention are listed below.

C. I. Pigment Yellow-1, 3, 12, 13, 14, 17, 81, 83, 87, 95, 109, 42
C. I. Pigment Orange-16, 36, 38
C. I. Pigment Red-5, 22, 38, 48: 1, 48: 2, 48: 4, 49: 1, 53: 1, 57: 1, 63: 1, 144, 146, 185, 101
C. I. Pigment Violet-19, 23
C. I. Pigment Blue-15: 1, 15: 3, 15: 4, 18, 60, 27, 29
C. I. Pigment Green-7, 36
C. I. Pigment White-6, 18, 21
C. I. Pigment Black-7
For the dispersion of the pigment, for example, a ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, paint shaker, or the like can be used. It is also possible to add a dispersant when dispersing the pigment. As the dispersant, a polymer dispersant is preferably used, and examples of the polymer dispersant include Solsperse series manufactured by Avecia. Also, a synergist according to various pigments can be used as a dispersion aid. These dispersants and dispersion aids are preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the pigment. The dispersion medium is used using a solvent or a polymerizable compound. However, the ink composition used in the present invention is preferably solvent-free because it reacts and cures immediately after ink landing. If the solvent remains in the cured image, the solvent resistance deteriorates and the VOC of the remaining solvent arises. Therefore, it is preferable in view of dispersibility that the dispersion medium is not a solvent but a polymerizable compound, and among them, a monomer having the lowest viscosity is selected.

  The pigment is preferably dispersed so that the average particle diameter of the pigment particles is 0.08 μm to 0.5 μm, and the maximum particle diameter is 0.3 μm to 10 μm, preferably 0.3 μm to 3 μm. Select the dispersion medium, dispersion conditions, and filtration conditions as appropriate. By controlling the particle size, clogging of the head nozzle can be suppressed, and ink storage stability, ink transparency, and curing sensitivity can be maintained.

  In the ink composition of the present invention, the colorant concentration is preferably 1% by mass to 10% by mass of the entire ink.

  In the present invention, a thermal base generator can also be used for the purpose of improving ejection stability and storage stability.

  Examples of the thermal base generator include compounds that release amines by decomposition by reactions such as organic acid and base salts that are decomposed by decarboxylation by heating, intramolecular nucleophilic substitution reaction, Rossen rearrangement, Beckmann rearrangement, etc. Those which cause some kind of reaction by heating and release a base are preferably used. Specifically, a salt of trichloroacetic acid described in British Patent No. 998,949, a salt of alpha-sulfonylacetic acid described in US Pat. No. 4,060,420, JP-A-59-157737 Salt of propylene acid described in the above, 2-carboxycarboxamide derivative, salt of the base component described in JP-A-59-168440 with thermally decomposable acid using alkali metal or alkaline earth metal in addition to organic base, Examples thereof include hydroxam carbamates utilizing the Rosen rearrangement described in JP-A No. 59-180537, and aldoxime carbamates described in JP-A No. 59-195237 that generate a nitrile by heating. In addition, British Patent No. 998,945, U.S. Pat. No. 3,220,846, British Patent No. 279,480, JP-A-50-22625, 61- No. 32844, 61-51139, 61-52638, 61-51140, 61-53634 to 61-53640, 61-55644, 61-55645 The thermal base generator described in each of the publications is useful.

  Furthermore, specific examples include guanidine trichloroacetate, methylguanidine trichloroacetate, potassium trichloroacetate, phenylsulfonylacetate guanidine, p-chlorophenylsulfonylacetate guanidine, p-methanesulfonylphenylsulfonylacetate guanidine, phenylpropiolate potassium, phenylpropiolate. There are guanidine allate, cesium phenylpropiolate, guanidine p-chlorophenylpropiolate, guanidine p-phenylene-bis-phenylpropiolate, tetramethylammonium phenylsulfonylacetate, and tetramethylammonium phenylpropiolate. The thermal base generator can be used in a wide range.

  The ink composition of the present invention newly generates an acid by an acid generated by actinic ray irradiation which has been already known, including JP-A-8-248561 and JP-A-9-34106. It is also possible to contain an acid proliferating agent.

  The ink composition of the present invention is produced by well dispersing a pigment together with a polymerizable composition and a pigment dispersant using a normal dispersing machine such as a sand mill. It is preferable to prepare a concentrated solution having a high pigment concentration in advance and dilute with a polymerizable composition. Sufficient dispersion is possible even with dispersion by a normal disperser, so it does not take excessive dispersion energy and does not require a great amount of dispersion time. Ink excellent in the quality is prepared. The ink is preferably filtered through a filter having a pore diameter of 3 μm or less, more preferably 1 μm or less.

  The ink composition of the present invention has a viscosity at 25 ° C. of more than 5 mPa · s and 40 mPa · s from the viewpoint of preventing a decrease in the followability of discharge and improving the discharge stability in a high-frequency head. It is preferable to adjust so that it may become below. Furthermore, the viscosity at 25 ° C. is preferably adjusted to 7 mPa · s to 80 mPa · s, and more preferably adjusted to 7 mPa · s to 40 mPa · s. An ink having a viscosity at 25 ° C. of 7 mPa · s to 40 mPa · s exhibits stable ejection characteristics even from a normal head having a frequency of 4 kHz to 10 kHz and a high frequency head of 10 to 50 KHz.

  In addition, the ink composition of the present invention preferably has an electric conductivity of 10 μS / cm or less in a piezo head and does not cause electrical corrosion inside the head. Further, in the continuous type, it is necessary to adjust the electric conductivity by the electrolyte. In this case, it is necessary to adjust the electric conductivity to 0.5 mS / cm or more.

  In the present invention, ink ejection (also referred to as ejection), light irradiation, heating, and the like are performed while controlling the viscosity and moisture content of the ink, and a uniform dot diameter can be obtained for various supports. Although it is required, the surface tension at 25 ° C. of the ink is 25 mN / m to 40 mN from the viewpoint of performing stable emission (also referred to as ejection) and obtaining a desired dot diameter even in the above case. / M is preferable.

  In order to adjust the surface tension, a surfactant may be contained as necessary. Examples of the surfactant preferably used in the ink composition of the present invention include anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, and fatty acid salts, polyoxyethylene alkyl ethers, and polyoxyethylene. Nonionic surfactants such as alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene block copolymers, cationic surfactants such as alkylamine salts and quaternary ammonium salts, interfaces having a polymerizable group Active compounds and the like. Of these, particularly preferable are surface active compounds having a polymerizable group such as an unsaturated bond, oxirane, or oxetane ring, such as silicone-modified acrylate, fluorine-modified acrylate, silicone-modified epoxy, fluorine-modified epoxy, silicone-modified oxetane, and fluorine-modified oxetane. .

  Various additives other than those described above can be used in the ink composition of the present invention. For example, leveling additives, matting agents, polyester resins for adjusting film properties, polyurethane resins, vinyl resins, acrylic resins, rubber resins, and waxes can be added. In order to improve the adhesion with the recording medium, it is also effective to add a trace amount of organic solvent. In this case, it is effective to add in a range that does not cause the problem of solvent resistance and VOC, and the amount used is in the range of 0.1% by mass to 5% by mass, preferably 0.1% by mass to 3% by mass. %. It is also possible to combine a radically polymerizable monomer and an initiator into a radical / cation hybrid type curable ink.

<Image forming method>
The image forming method of the present invention will be described.

  In the image forming method of the present invention, the ink composition of the present invention is ejected and drawn on a recording material by an inkjet recording method, and then irradiated with actinic rays such as ultraviolet rays, or heated to heat the ink composition ( (Also referred to simply as ink).

  In the image forming method of the present invention, it is preferable that the ink is heated together with the inkjet nozzles during ink ejection (also referred to as ejection) to lower the viscosity of the ink liquid. The heating temperature is 35 ° C to 100 ° C, preferably 35 ° C to 60 ° C.

  In the present invention, the total ink film thickness after the ink has landed and cured by irradiation with actinic rays is preferably 2 μm to 20 μm. In the ink composition jet recording in the screen printing field, the total ink film thickness currently exceeds 20 μm, but in the flexible packaging printing field where the recording material is often a thin plastic material, Not only because of the curl / wrinkle problem, but also the problem that the entire print will have a slight change in texture and texture. Moreover, in this invention, it is preferable that the amount of droplets discharged from each nozzle is 2 to 15 pl.

  In the present invention, in order to form a high-definition image, it is preferable that the irradiation timing is as early as possible. However, in the present invention, the light irradiation is started at a timing at which the viscosity or water content of the ink is in a preferable state. Is preferred.

  Specifically, as the irradiation condition of the generated light, actinic light irradiation is preferably started between 0.001 second and 1.0 second after ink landing, and more preferably 0.001 second to 0.4 second. Further, it is preferable that the irradiation is terminated after 0.1 seconds to 3 seconds, preferably within 0.2 seconds to 1 second, until the ink fluidity is lost. By setting it as the above condition, enlargement of the dot diameter and bleeding between the dots can be prevented.

  As a method for irradiating actinic rays, the basic method is disclosed in JP-A-60-132767. According to this, the light source is provided on both sides of the recording head unit, and the recording head and the light source are scanned by the shuttle method. Irradiation is performed after a certain period of time after ink landing. Further, the curing is completed by another light source that is not driven. In US Pat. No. 6,145,979, as an irradiation method, a method using an optical fiber or a method of irradiating a recording unit with UV light by applying a collimated light source to a mirror surface provided on the side surface of the recording head unit. It is disclosed. Any of these irradiation methods can be used in the image forming method of the present invention.

  Also, the method of irradiating actinic rays in two stages, first irradiating actinic rays by the method described above between 0.001 seconds and 1.0 seconds after ink landing, and further irradiating actinic rays after all printing is completed Is also a preferred embodiment. By dividing the irradiation of actinic rays into two stages, it is possible to further suppress the shrinkage of the recording material that occurs during ink curing.

Examples of light sources used for actinic ray irradiation include mercury arc lamps, xenon arc lamps, fluorescent lamps, carbon arc lamps, tungsten-halogen copying lamps, high pressure mercury lamps, metal halide lamps, electrodeless UV lamps, low pressure mercury lamps, and UV lasers. , Xenon flash lamps, insect traps, black lights, germicidal lamps, cold cathode tubes, LEDs, and the like, but are not limited to these. Among these, fluorescent tubes are preferred because of their low energy and low cost. A light source having a light emission wavelength peak at 250 nm to 370 nm, preferably 270 nm to 320 nm is preferable in terms of sensitivity. Illuminance ^{1mW / cm 2 ~3000mW / cm 2} , preferably from ^{1mW / cm 2 ~200mW / cm 2} . Further, in the case of curing with an electron beam, it is usually cured with an electron beam having an energy of 300 eV or less, but it can also be cured instantaneously with an irradiation amount of 1 to 5 Mrad.

  The ink composition of the present invention is used to print an image on a recording medium (also referred to as a base material). As the recording medium, all of a wide range of conventional synthetic resins used in various applications can be used. Specific examples include polyester, polyvinyl chloride, polyethylene, polyurethane, polypropylene, acrylic resin, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polybutadiene terephthalate, and the like. The thickness and shape of the resin base material are not limited at all.

  As a base material that can be used in the present invention, a non-absorbent support can be used in addition to normal uncoated paper, coated paper, etc. Among them, a non-absorbent support is used as the base material. Is preferred.

  In the present invention, various non-absorbing plastics and films thereof can be used as the non-absorbing support. Examples of the various plastic films include PET film, OPS film, OPP film, ONy film, PVC film, A PE film and a TAC film can be mentioned. As other plastics, polycarbonate, acrylic resin, ABS, polyacetal, PVA, rubbers and the like can be used. Moreover, it is applicable also to metals and glass. Among these recording materials, the configuration of the present invention is effective particularly when an image is formed on a PET film, an OPS film, an OPP film, an ONy film, or a PVC film that can be shrunk by heat. These base materials are not only susceptible to curling and deformation of the film due to the curing shrinkage of the ink and the heat generated during the curing reaction, but also the ink film is difficult to follow the shrinkage of the base material.

  The surface energies of these various plastic films differ greatly, and it has been a problem in the past that the dot diameter after ink landing varies depending on the recording material. The constitution of the present invention includes an OPP film having a low surface energy, an OPS film, and a PET having a relatively large surface energy, but the substrate preferably has a wetting index of 40 mN / m to 60 mN / m.

  In the present invention, it is more advantageous to use a long (web) recording material in terms of the cost of the recording material such as packaging cost and production cost, the production efficiency of the print, and the ability to cope with printing of various sizes. is there.

<Inkjet recording device>
Next, the ink jet recording apparatus of the present invention will be described.

  The ink jet recording apparatus of the present invention will be described below with reference to the drawings as appropriate. Note that the recording apparatus of the drawings is merely one aspect of the inkjet recording apparatus of the present invention, and the inkjet recording apparatus of the present invention is not limited to this drawing.

  FIG. 1 is a front view showing a configuration of a main part of the ink jet recording apparatus of the present invention. The recording apparatus 1 includes a head carriage 2, a recording head 3, an irradiation unit 4, a platen unit 5, and the like. In the recording apparatus 1, the platen unit 5 is installed under the recording material P. The platen unit 5 has a function of absorbing ultraviolet rays, and absorbs excess ultraviolet rays that have passed through the recording material P. As a result, a high-definition image can be reproduced very stably.

  The recording material P is guided by the guide member 6 and moves from the near side to the far side in FIG. 1 by the operation of the conveying means (not shown). A head scanning unit (not shown) scans the recording head 3 held by the head carriage 2 by reciprocating the head carriage 2 in the Y direction in FIG.

  The head carriage 2 is installed on the upper side of the recording material P, and stores a plurality of recording heads 3 to be described later according to the number of colors used for image printing on the recording material P, with the discharge ports arranged on the lower side. The head carriage 2 is installed with respect to the main body of the recording apparatus 1 in such a manner that it can reciprocate in the Y direction in FIG. 1, and reciprocates in the Y direction in FIG. 1 by driving the head scanning means.

  In FIG. 1, the drawing is shown on the assumption that the head carriage 2 houses the recording heads 3 of white (W), yellow (Y), magenta (M), cyan (C), black (K), and white (W). In practice, the number of colors of the recording head 3 housed in the head carriage 2 can be determined as appropriate.

  The recording head 3 is discharged from an ejection port by the operation of ejection means (not shown) provided in a plurality of ink compositions (for example, ultraviolet curable ink) supplied by an ink supply means (not shown). The ink is discharged toward the recording material P. The ultraviolet curable ink ejected by the recording head 3 is composed of a coloring material, a polymerizable monomer, an initiator, and the like, and is a monomer associated with the initiator acting as a catalyst when irradiated with ultraviolet rays. It has the property of being cured by crosslinking and polymerization reactions.

  During the scanning in which the recording head 3 moves from one end of the recording material P to the other end of the recording material P in the Y direction in FIG. 1 by driving the head scanning means, a certain area (landing possible area) in the recording material P On the other hand, ultraviolet curable ink is ejected as ink droplets, and the ink droplets are landed on the landable area.

  The above scanning is performed as many times as necessary, and after the ultraviolet curable ink is discharged toward one landing possible region, the recording material P is appropriately moved from the front to the back in FIG. While performing the scanning, the recording head 3 discharges the ultraviolet curable ink to the next landable area adjacent to the rearward direction in FIG.

  By repeating the above-described operation and ejecting the ultraviolet curable ink from the recording head 3 in conjunction with the head scanning means and the conveying means, an image composed of an aggregate of ultraviolet curable ink droplets is formed on the recording material P.

  The irradiation unit 4 includes an ultraviolet lamp that emits ultraviolet light in a specific wavelength region with stable exposure energy and a filter that transmits ultraviolet light of a specific wavelength. Here, as the ultraviolet lamp, a mercury lamp, a metal halide lamp, an excimer laser, an ultraviolet laser, a cold cathode tube, a black light, an LED (light emitting diode), etc. can be applied, and a strip-shaped metal halide lamp tube, cold cathode tube, A mercury lamp tube or black light is preferred. In particular, a cold cathode tube and black light emitting ultraviolet light having a wavelength of 365 nm are preferable because they can prevent bleeding, control dot diameter efficiently, and reduce wrinkles during curing. By using black light as the radiation source of the irradiation means 4, the irradiation means 4 for curing the ultraviolet curable ink can be produced at low cost.

  The irradiating means 4 is almost the largest one that can be set by the recording apparatus (ultraviolet curable ink jet printer) 1 among the landable areas in which the recording head 3 ejects the ultraviolet curable ink by one scan driven by the head scanning means. It has the same shape or a shape larger than the landable area.

  The irradiation means 4 is fixed on both sides of the head carriage 2 so as to be substantially parallel to the recording material P.

  As described above, as a means for adjusting the illuminance of the ink discharge portion, not only the entire recording head 3 is shielded, but in addition, the ink discharge of the recording head 3 is determined from the distance h1 between the irradiation means 4 and the recording material P. It is effective to increase the distance h2 between the portion 31 and the recording material P (h1 <h2), or to increase the distance d between the recording head 3 and the irradiation means 4 (d is increased). Further, it is more preferable to provide a bellows structure 7 between the recording head 3 and the irradiation means 4.

  Here, the wavelength of the ultraviolet rays irradiated by the irradiation means 4 can be changed as appropriate by replacing the ultraviolet lamp or filter provided in the irradiation means 4.

  FIG. 2 is a diagram illustrating another example of the configuration of the main part of the ink jet recording apparatus.

  The ink jet recording apparatus shown in FIG. 2 is called a line head system, and a plurality of ink jet recording heads 3 of each color are fixedly arranged on the head carriage 2 so as to cover the entire width of the recording material P. ing. The head carriage 2 is shielded from light.

  On the other hand, on the downstream side of the head carriage 2, there is provided irradiation means 4 arranged so as to cover the entire width of the recording material P and cover the entire area of the ink printing surface. As the ultraviolet lamp used in the illuminating means 4, the same one as described in FIG. 1 can be used.

  In this line head system, the head carriage 2 and the irradiating means 4 are fixed, and only the recording material P is conveyed, and ink ejection and curing are performed to form an image.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

Example 1
<< Preparation of polymerizable composition >>
A polymerizable compound and a polymerization initiator were added as shown in Tables 1 and 2, and dissolved in 50 parts by mass of methylene chloride to prepare a polymerizable composition.

<< Polymerization of polymerizable composition >>
The composition was polymerized by applying active light or heat to the prepared polymerizable composition as shown in Table 2.

<Polymerization by irradiation with actinic rays>
Actinic rays were irradiated for 20 minutes from a high-pressure mercury lamp placed on a container containing the polymerizable composition.

《Polymerization by heating》
The polymerizable composition was placed in a container equipped with a refluxer and heated to reflux for 20 minutes.

<< Evaluation of polymerizable composition >>
<Evaluation of polymerizability>
After the polymer was collected from the reaction solution by filtration and dried, the mass of the obtained polymer was measured to calculate the yield, and the polymerizability of the polymerizable composition was evaluated.

<Evaluation of polymerizability under high humidity conditions>
The polymerizable composition is polymerized in an atmosphere with a humidity of 80%, the residue is washed away with a solvent and dried, and then the mass of the obtained polymer is measured to calculate the yield, which is used as the polymerizable composition. The polymerizability under high humidity conditions was evaluated.

<< Evaluation criteria for polymerizability >>
A with a yield of more than 80%, A with a yield of more than 60% and 80% or less, C with a yield of more than 40% and 60% or less, D with a yield of more than 20% and 40% or less, 20% or less was designated E. The higher the yield, the higher the polymerizability.

<< Evaluation of preservability of polymerizable composition >>
After storing the polymerizable composition at 70 ° C. for 3 days, the composition was shaken if necessary, and the coloration and thickening of the composition were visually evaluated as follows.

A: No coloring or thickening,
○: Some coloring and thickening were observed,
Δ: A considerable coloring or thickening was observed,
X: The degree of coloring or thickening was remarkable,
However, Sample No. using trifluoromethanesulfonic acid as the polymerizable initiator was used. 101 and comparative sample no. For 101, the storage stability was not evaluated.

  The evaluation results of the polymerizable composition are shown in Tables 1 and 2.

  The compounds used are shown below.

<Epoxy compound>
Miasendioxide: Celoxide 3000: Daicel Chemical Industries, Ltd. Tarpinolene Dioxide: ATOFINA, Inc. <Oxetane compound>
OXT-221: Toagosei Co., Ltd. OXT-212: Toagosei Co., Ltd. <Polymerization initiator>
UVI-6992: Propion carbonate solution manufactured by Dow Chemical Co., Ltd. WPI-113: Propion carbonate solution manufactured by Wako Pure Chemical Industries, Ltd. The molecular weight of the compound represented by the general formula (X) according to the present invention used is as follows.
X-1: 252.35, X-3: 338.48, X-5: 282.42
X-21: 226.31, X-28: 240.30, X-38: 324.50
X-55: 480.63, X-63: 410.59, X-64: 266.38
X-65: 268.39, X-72: 394.59, X-74: 380.52
X-75: 622.37.

Example 2
<< Preparation of polymerizable composition >>
A polymerizable compound, an acid generator and a basic compound were dissolved as shown in Tables 3 and 4 to prepare a polymerizable composition.

  The compounds used are shown below.

[Basic compounds]
Basic compound A: N-ethyldiethanolamine Basic compound B: Triisopropanolamine

<< Production of cured film >>
After applying the polymerizable composition to synthetic paper (synthetic paper YUPO FGS manufactured by YUPO Corporation) to a film thickness of 3 μm, the cured film was irradiated with 800 mJ / cm ² of UV light with a metal halide lamp within one second. Obtained.

<< Evaluation of cured film >>
The physical properties of the obtained cured film were evaluated by the following tests. (1) Pencil Scratch Test According to JIS K 5400, the hardness of each cured film was measured.

As for the rank of hardness, 6B is the softest and 9H is the hardest in the order of (soft) 6B to B, HB, F, H to 9H (hard). (2) Substrate tape peeling residual adhesion rate test Adhesive tape (Scotch # 250, manufactured by Sumitomo 3M) was attached to the cured composition sample obtained in the cross-cut test of JIS K 5400, and a 2 kg roller. Then, the sample was peeled off at once, and the number of remaining grid-like samples was investigated. (3) Evaluation of flexibility The obtained cured film was evaluated in accordance with the method for evaluating bending resistance defined in JIS K 5600.

<< Evaluation of viscosity of polymerizable composition >>
The viscosity of each prepared polymerizable composition was measured using a rheometer MCR300 (manufactured by Physica) under the conditions of a temperature of 25 ° C. and a Shear Rate = 1000 (1 / s), and rank evaluation was performed as follows.

A: A composition having a viscosity at 25 ° C. of 150 mPa · s or less,
○: 150 mPa · s to 300 mPa · s composition,
(Triangle | delta): The composition of 300 mPa * s-500 mPa * s,
×: Composition of 500 mPa · s or more,
<< Evaluation of cured film storage stability >>
The obtained cured composition was tested in the same manner as described above for the pencil scratch test and flexibility evaluation of the cured composition after being stored for 1 month in a high-temperature and high-humidity environment at 85 ° C. and 90% RH. The rank was evaluated as follows.

◎: There is no significant change in test results,
○: Some deterioration is observed but there is no practical problem.
△: Deterioration observed x: Deterioration greatly observed x
Note that ◎ and ○ are practically no problem levels.

<< Evaluation of durability against temperature change of cured film >>
《Durability test (adhesion)》
The obtained cured film was stored at 85 ° C. for 30 minutes and stored at −40 ° C. for 30 minutes, and then the surface of the cured film was rubbed to test whether the cured film was peeled off. Was ranked as follows.

When the cured film is peeled off or repeated until it reaches 10 cycles without peeling off,
X: The number of cycles when peeling off is 3 or less,
Δ: 4 or more and 6 or less,
○: 7 to 10
◎: not peeled off,
Note that ◎ and ○ are not problematic in practical use.

《Durability test (flexibility)》
The obtained cured film is stored at 85 ° C. for 30 minutes, and stored at −40 ° C. for 30 minutes, and then the cured film is bent to test whether the cured film is cracked or not. Property). The cured film was repeatedly cracked until it reached 10 cycles without cracking, and rank evaluation was performed as follows.

×: The number of cycles when cracks are 3 or less,
Δ: 4 or more and 6 or less,
○: 7 to 10
◎: No cracks ◎,
Note that ◎ and ○ are not problematic in practical use.

  The results obtained are shown in Table 5.

  From Table 5, the samples of the present invention have sufficient adhesion and hardness, the cured film retains hardness and flexibility even after long-term storage, there is almost no deterioration, and durability against temperature changes It turns out that it is excellent.

Example 3
<Ink composition>
5 parts by mass of a dispersant (PB822 manufactured by Ajinomoto Fine Techno Co., Ltd.) and each photopolymerizable compound described in Tables 6 and 7 were placed in a stainless steel beaker and stirred for 1 hour while heating on a 65 ° C hot plate. , Mixed and dissolved. Next, after adding 3 parts by mass of various pigments to this solution, it was sealed in a plastic bottle together with 200 g of zirconia beads having a diameter of 1 mm, and subjected to a dispersion treatment with a paint shaker for 2 hours. Next, the zirconia beads are removed, and various additives such as photopolymerization initiators, basic compounds, and surfactants are added in combinations shown in Tables 6 and 7, and 0.8 μm is added to prevent printer clogging. The ink composition set was prepared by filtration through a membrane filter.

The pigments used were as follows: K: CI pigment black 7
C: CI pigment Blue 15: 3
M: CI pigment Red 57: 1
Y: CI pigment Yellow 13
W: Titanium oxide (anatase type: particle size 0.2 μm)
Lk: CI pigment black 7
Lc: CI pigment Blue 15: 3
Lm: CI pigment Red 57: 1
Ly: CI pigment Yellow 13
The compounds used are as follows.

F178k: Megafax F178k
Perfluoroalkyl group-containing acrylic oligomer (Dainippon Ink and Chemicals)
F1405: Megafax F1405
Perfluoroalkyl group-containing ethylene oxide adduct (Dainippon Ink Chemical Co., Ltd.)
R100: Haritac R100 (Rosin-modified maleic resin, Harima Chemical Co., Ltd.)
145P: Halitack 145P (Rosin-modified maleic resin, Harima Chemical Co., Ltd.)

<< Inkjet image forming method >>
Each ink composition prepared above is loaded into an ink jet recording apparatus having the structure shown in FIG. 1 having a piezoelectric ink jet nozzle, and the following image recording is performed on each recording material having a width of 600 mm and a length of 20 m. Was performed continuously. The ink supply system was composed of an ink tank, a supply pipe, a front chamber ink tank just before the head, a pipe with a filter, and a piezo head. The ink was insulated from the front chamber tank to the head portion and heated at 50 ° C. In addition, the head portion is heated according to the viscosity of each curable composition ink, and multi-size dots having a droplet amount of 2 pl to 15 pl are set to 720 × 720 dpi (dpi is 1 inch, that is, the number of dots per 2.54 cm). The ink composition described above was continuously ejected by being driven so that it could be ejected at a resolution of (shown). The recording material was heated to 50 ° C. by a surface heater. After landing, irradiation light source A on both sides of the carriage: high-pressure mercury lamp VZero085 (manufactured by INTEGRATION TECHNOLOGY) or irradiation light source B: metal halide lamp (manufactured by Nippon Battery Co., Ltd. MAL400NL power = 3 kW · hr 120 W / cm) (after landing) (Less than 0.4 seconds). When the total ink film thickness was measured after image recording, it was in the range of 2.3 μm to 13 μm. The inkjet image was formed by printing in an environment of 27 ° C. and 85% RH and 25 ° C. and 25% RH according to the above method.

  In addition, the illumination intensity of each irradiation light source measured the integrated illumination intensity of 254 nm using UVPF-A1 by Iwasaki Electric Co., Ltd.

  The details of the abbreviations of the recording materials described are as follows.

Synthetic paper: Synthetic paper manufactured by YUPO Corporation YUPO FGS
PVC: polyvinyl chloride
<Evaluation of ink viscosity>
The viscosity of each prepared ink was measured using a rheometer MCR300 (manufactured by Physica) under the conditions of a temperature of 25 ° C. and a Shear Rate = 1000 (1 / s), and rank evaluation was performed as follows.

A: ink having a viscosity at 25 ° C. in the range of 7 mPa · s to 40 mPa · s,
○: Ink of more than 40 mPa · s and less than 80 mPa · s ×: Ink of 80 mPa · s or more,
<Evaluation of ink ejection properties>
After the ink was continuously discharged for 30 minutes, the following rank evaluation was performed on the condition of ink shortage visually.

◎: Good level with no defects,
○: There is a shortage, but there is no problem,
△: There is a lack, level that affects image quality,
×: Unacceptable level due to frequent defects
In addition, ◎ and ○ are practically no problem levels.
<Evaluation of inkjet recording image>
Each image recorded by the above image forming method was subjected to the following evaluations.
A 6-point MS Mincho type character was printed at the target density, and the character roughness was enlarged and evaluated with a loupe, and character quality was evaluated according to the following criteria.

◎: No roughness ○: Slight rustiness is visible △: Gashesiness is visible, but it can be recognized as characters and can be used at the last minute ×: Slightly rustling, characters are faint and unusable ◎ and ○ have no practical problems Is a level.

《Color mixing (bleeding, wrinkle)》
Print at 720 dpi so that each dot of Y, M, C, K colors is adjacent to each other, enlarge each adjacent color dot with a magnifying glass, visually observe the state of bleeding and wrinkles, and evaluate color mixing according to the following criteria Went.

◎: Adjacent dot shape keeps perfect circle and no blur ○: Adjacent dot shape keeps almost perfect circle and almost no blur △: Adjacent dots are slightly blurred and dot shape is slightly displaced , Barely usable level ×: Adjacent dots are smeared and mixed, and wrinkles are generated in the overlapping portion, and cannot be used. ◎ and ◯ are levels with no practical problems.

<< Evaluation of cured film hardness and bending resistance of cured film >>
The physical properties of a cured film prepared by printing by the above-described inkjet image forming method using magenta ink in which a magenta pigment is dispersed were evaluated by the following tests. (1) Pencil scratch test: The hardness of each cured film was measured according to JIS K 5400. As for the rank of hardness, 6B is the softest and 9H is the hardest in the order of (soft) 6B to B, HB, F, H to 9H (hard). (2) Evaluation of flexibility: After the ink was applied onto PVC by injection coating so as to have a film thickness of 3 μm, 800 mJ / cm ² of ultraviolet light was irradiated within 1 second with a metal halide lamp to obtain a cured film. The obtained cured film was evaluated in accordance with the method for evaluating the bending resistance of JIS K 5600.

<Evaluation of ink storage stability>
The prepared ink was put in a sealed container and stored in a dark place at room temperature for 1 month, and then an ink jet image was formed by the above image forming method, and the storage stability was ranked as follows.

○: No significant change in test results after storage for 1 month
△: A large variation was observed in one or more items in any test,
×: The ink viscosity increased and image formation could not be performed.
In addition, (circle) is the storage stability which does not have a problem practically.

  Here, “any test” refers to any one test selected from ink viscosity, ink ejection property, ink jet recording image evaluation, color mixing, cured film hardness, and cured film bending resistance evaluation. .

<< Evaluation of cured film storage stability >>
The obtained ink cured composition was stored in a high-temperature and high-humidity environment at 85 ° C. and 90% RH for 1 month, and then the pencil scratch test and the evaluation of flexibility of the cured composition were performed in the same test as described above. evaluated.

◎: There is no significant change in test results,
○: Some deterioration is observed but there is no practical problem.
Δ: Deterioration observed
X: Significant degradation was observed. Note that ◎ and ○ are practically satisfactory levels.

<< Evaluation of durability against temperature change of cured film >>
《Durability test (adhesion)》
The obtained ink cured film was stored at 85 ° C. for 30 minutes and stored at −40 ° C. for 30 minutes, and then the surface of the cured film was rubbed to test whether the cured film peeled off. ). This was repeated until the cured film peeled off or reached 10 cycles without peeling off, and the rank evaluation was performed as follows.

X: The number of cycles when peeling off is 3 or less,
Δ: 4 to 6
○: ○ from 7 to 10
◎: What does not peel off ◎,
Note that ◎ and ○ are not problematic in practical use.

《Durability test (flexibility)》
The obtained ink cured film was stored at 85 ° C. for 30 minutes and stored at −40 ° C. for 30 minutes, and then the cured film was bent to test whether the cured film was cracked or not. Property). This was repeated until cracks entered the cured film or 10 cycles were reached without cracks, and the rank evaluation was performed as follows.

×: The number of cycles when cracks are 3 or less,
Δ: 4 or more and 6 or less,
○: 7 to 10
◎: No cracks,
Note that ◎ and ○ are not problematic in practical use.

  The results are shown in Table 8.

  From Table 8, it can be seen that the sample of the present invention has good injection properties and improved image quality. It turns out that the sample of this invention shows favorable sclerosis | hardenability irrespective of the difference in an environment. It can be seen that the sample of the present invention maintains various performances and physical properties even after long-term storage. Furthermore, it can be seen that the sample of the present invention is excellent in durability against temperature change.

Claims (15)

A polymerizable composition comprising a compound having a molecular weight of 180 to 1000 represented by the following general formula (X).

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or an alkyl group, and R ³ is a saturation to which R ¹ and R ² in the general formula (X) are bonded. It is a substituent bonded at an arbitrary position of the hydrocarbon ring, and n is an integer from 0 to 7. When n is plural, R ³ may be the same as or different from each other. Is a (p + 1) -valent linking group or a simple bond bonded at any position to the saturated hydrocarbon ring to which R ¹ and R ² in general formula (X) are bonded, and p is 1 to 3 Q is an integer from 1 to 3. When p is plural, plural R ⁴ , R ⁵ and R ⁶ may be the same or different from each other, and plural q In this case, a plurality of L, R ⁴ , R ⁵ and R ⁶ may be the same or different from each other.) The polymerizable composition according to claim ¹ , wherein at least one of R ¹ and R ² is an alkyl group. The polymerizable composition according to claim 1 or ² , wherein one of R ¹ and R ² is an alkyl group and the other is a hydrogen atom. The polymerizable composition according to any one of claims 1 to 3, wherein ^{one of} R ¹ and R ² is an alkyl group having 1 to 3 carbon atoms and the other is a hydrogen atom. The polymerizable composition according to any one of claims 1 to 4, wherein R ⁵ and R ⁶ are each an alkyl group. The polymerizable composition according to any one of claims 1 to 5, further comprising an acid generator. An ink composition comprising the polymerizable composition according to any one of claims 1 to 6. The ink composition according to claim 7, wherein the viscosity at 25 ° C is 7 mPa · s to 40 mPa · s. The ink composition according to claim 7 or 8, further comprising a pigment. An image forming method in which the ink composition according to any one of claims 7 to 9 is jetted onto a recording material in an image-like manner from an inkjet recording head, and printing is performed on the recording material. The ink composition is cured through a step of heating after the ink composition has landed, or a step of irradiating actinic rays for 0.001 seconds to 1.0 seconds. . 11. The image forming method according to claim 10, wherein a minimum ink droplet amount ejected from a nozzle of the inkjet recording head is 2 pl to 15 pl. An ink jet recording apparatus used in the image forming method according to claim 10 or 11, wherein the ink is discharged after the recording head is heated to 35 ° C to 100 ° C. Inkjet recording device. An ink jet recording apparatus for use in the image forming method according to claim 10 or 11, wherein the recording medium is heated to 35 ° C to 60 ° C when the ink composition is ejected. Inkjet recording apparatus. The compound characterized by the molecular weight represented by the following general formula (X-A) being 180-1000.

(Wherein R ¹¹ , R ¹² , R ¹⁵ and R ¹⁶ represent a hydrogen atom or an alkyl group, and R ¹³ represents an alkyl bonded to an arbitrary position of the saturated hydrocarbon ring in the general formula (X-A)). M represents an integer of 0 to 7, R ¹⁴ represents a hydrogen atom or an alkyl group, L ² is bonded to an arbitrary position of the saturated hydrocarbon ring in the general formula (X-A), An alkylene group, an oxygen atom, or a divalent linking group formed by a combination of the alkylene group and the oxygen atom.) The compound according to claim 14, wherein the general formula (X-A) is represented by the following general formula (X-B).

(Wherein R ²⁵ and R ²⁶ each represents an alkyl group, R ²⁴ represents a hydrogen atom or an alkyl group, and L ³ represents an alkylene group, an oxygen atom, or a combination of the alkylene group and the oxygen atom. Represents a divalent linking group to be formed.)

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