JP4673281B2 - Active energy ray curable non-aqueous resin composition, UV curable non-aqueous resin composition - Google Patents

Description

  The field in which the present invention is used is a field that requires an active energy ray-curable resin composition having both a high curing speed and excellent mechanical properties.

  Conventionally, ultraviolet curable resin compositions have been used as coating films for optical fibers. As the resin composition, there is provided a material having excellent curability by ultraviolet rays and a material having excellent toughness and excellent mechanical properties such as flexibility.

  As such a material, it is generally known to use polyurethane (meth) acrylate. This is obtained by reacting 1 mol of an oligomer containing both isocyanate groups synthesized by polyaddition reaction of glycol and a diisocyanate compound with 2 mol of a hydroxyl group-containing (meth) acrylate monomer such as hydroxyalkyl (meth) acrylate. Manufactured. When the molecular weight of the polyurethane (meth) acrylate is increased, the content of unsaturated groups contained in one molecule is decreased and curability (the molecular weight between crosslinks is increased) is deteriorated. On the other hand, when the molecular weight of the oligomer is decreased. In particular, the elongation percentage of the film is lowered and the mechanical properties are deteriorated, so that both the curability and the mechanical properties cannot be satisfied.

  In addition, in the polyurethane (meth) acrylate described above, some triol compounds may be used in combination with glycol, or some triisocyanate compounds may be used in combination with diisocyanate compounds to branch the oligomer skeleton and contain unsaturated groups. A composition that improves the curability by increasing the amount is also known, but such a film has a problem that the elongation rate is low, so that the mechanical properties are inferior, and the viscosity of the composition becomes high.

  Provided is an active energy ray-curable resin composition that combines curability and excellent mechanical properties that could not be achieved by conventional techniques.

  As a means for solving the above problems, the present invention has found that all of the above problems can be solved by using a specific resin composition, and has completed the present invention.

That is, the present invention
1. At the molecular end, the following general formula (AC) m- (PO)-(R1-O) p-OCHN-
(In the formula, AC represents a (meth) acryloyl group, PO represents a trivalent or higher polyol component residue, m represents m ≦ n−1 when PO uses a polyol component having an n valence, And m is an integer of 2 or 3, R1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and p represents an integer of 2 to 100.)
An active energy ray-curable non-aqueous resin composition comprising a reactive oligomer (A) having a functional group represented by formula (A) (but not having a salt group) ,
2. The active energy ray-curable non-aqueous resin composition according to item 1 , wherein in the reactive oligomer (A), the polyol component of the general formula is a tri- to tetravalent polyol component,
3. After the reactive oligomer (A) reacts a polyol component with (meth) acrylic acid to produce a hydroxyl group-containing polyfunctional (meth) acrylate monomer, the hydroxyl group reacts with a monoepoxide, and then obtained. 3. The active energy ray-curable non-aqueous resin composition according to 1 or 2, obtained by reacting the obtained reaction product with a (polymer) compound containing two or more isocyanate groups until the isocyanate value becomes 1 or less. ,
4. The ultraviolet curable non-aqueous resin composition according to any one of 1 to 3, which comprises the reactive oligomer (A) and the photopolymerization initiator (B).

  Since the composition of the present invention uses a urethane acrylate oligomer having a specific structure at the molecular end, it exhibits excellent curability and excellent mechanical properties by irradiation with active energy rays.

  The reactive oligomer (A) used in the present invention is represented by the above general formula. In the general formula, the polyol component forming the polyol component residue preferably includes trimethylolethane, trimethylolpropane, glycerin, diglycerin, pentaerythritol, dipentaerythritol, sorbitol and the like.

  In the general formula, examples of the divalent hydrocarbon group having 2 to 10 carbon atoms represented by R1 include aliphatic groups, aromatic groups, and a combination thereof. The hydrocarbon group may be linear or branched. The hydrocarbon group is specifically introduced by monoepoxide. Specific examples of the monoepoxide include, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,2-pentylene oxide, 1,2-octylene oxide, butadiene oxide, butyl glycidyl ether, hexyl glycidyl ether, Octyl glycidyl ether, dodecene oxide, allyl glycidyl ether, phenyl glycidyl ether, cyclohexene oxide, vinylcyclohexene monooxide, oxetane, tetrahydrofuran, styrene oxide, glycidyl acetate, glycidyl laurate, CARDURA E10 Glycidyl ester, manufactured by Shell Chemical Co., Ltd.).

  In the general formula, the urethane bond at the molecular end can be introduced by a polyisocyanate compound. Examples of polyisocyanates include hexamethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and lysine. Aliphatic diisocyanate compounds such as diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or −2,6) -) Diisocyanate, 1,3- (or 1,4-) di (isocyanatomethyl) cyclohexane, 1,4-cyclohe Alicyclic diisocyanate compounds such as sun diisocyanate, 1,3-cyclopentane diisocyanate, 1,2-cyclohexane diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, tetramethylxylylene diisocyanate, tolylene diisocyanate, 4,4'- Diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, (m- or p-) phenylene diisocyanate, 4,4 '-Biphenylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, bis (4-isocyanatophenyl) sulfone, isopropylidenebis (4-Phenyl isocyanate) aromatic diisocyanate compound, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 4 , 4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate and the like, polyisocyanate compounds having three or more isocyanate groups, burette type adducts, isocyanuric ring type adducts, and the like. .

  In the general formula, the remaining chain bonded to NH— may contain, in addition to the urethane bond, a bond such as an ester bond, an ether bond, an amide bond, or a hydrocarbon bond, or a combination of two or more thereof. Such a bond may be linear or branched. Furthermore, the remaining chain ends are unsaturated groups such as (meth) acryloyl groups, monovalent hydrocarbon groups such as methyl, ethyl, propyl, butyl, and phenyl groups, hydroxyl groups, isocyanate groups, carboxyl groups, And alkoxy groups.

  Preferred examples of the reactive oligomer (A) include the following.

(AC) 2- (TMP)-(PEO) -OCHN-A-NHCO-
(PEO)-(TMP)-(AC) 2,
(AC) 2- (TMP)-(PPO) -OCHN-A-NHCO-
(PEO)-(TMP)-(AC) 2,
(AC) 3- (PES)-(PEO) -OCHN-A-NHCO-
(PEO)-(PES)-(AC) 3,
(AC) 2- (G)-(PEO) -OCHN-A-NHCO-
(PEO)-(G)-(AC) 2,
(AC) 2- (TMP)-(PEO) -OCHN- (A-NHCO-
PEG-OCHN) p- (PEO)-(TMP)-(AC) 2,
(AC) 3- (PES)-(PPO) -OCHN- (A-NHCO-
PPG-OCHN) p- (PPO)-(PES)-(AC) 3,
(AC) 2- (TMP)-(PEO) -OCHN- (A-NHCO-PE
-OCHN) p- (PEO)-(TMP)-(AC) 2

  In the above formula, TMP is based on the trimethylolpropane component, PES is based on the pentaerythritol component, G is based on the glycerin component, PEO is based on the polymerization component of ethylene oxide, PPO is based on the polymerization component of propylene oxide, and A is poly PE is due to the isocyanate compound component, PE is due to the polyester resin component of both terminal hydroxyl groups, and p represents an integer of 1-100.

  The reactive oligomer (A) has a number average molecular weight in the range of 1,000 to 50,000, particularly 1,000 to 10,000. When the number average molecular weight is less than 1,000, the elongation percentage of the coating film is decreased. On the other hand, when the number average molecular weight exceeds 50,000, the viscosity is increased or the curability is decreased.

  The reactive oligomer (A) is obtained, for example, by reacting a polyol component with (meth) acrylic acid to produce a hydroxyl group-containing polyfunctional (meth) acrylate monomer, and then reacting the hydroxyl group with a monoepoxide. The reaction product can be produced by reacting the polyisocyanate compound (including the resin) so that substantially no free isocyanate groups remain. The above reaction can be produced by a conventionally known method. Moreover, a reaction catalyst can be used as needed.

  Specifically, for example, a mixture of a polyol component and acrylic acid in an inert organic solvent (such as an aromatic hydrocarbon) in the presence of a polymerization inhibitor (such as hydroquinone) or an esterification catalyst (such as a sulfonic acid or a metal catalyst). A polyfunctional (meth) acrylate monomer is produced by an esterification reaction at a reaction temperature of 100 to 300 ° C. so that an average of about one hydroxyl group remains in the molecule. The esterification reaction can be managed by measuring the acid value. Next, an inert organic solvent is removed from the reaction product under reduced pressure, and a necessary amount of monoepoxide is added to the reaction product and reacted to produce a polyether polyfunctional (meth) acrylate monomer having a terminal hydroxyl group.

  Next, a polyfunctional (meth) acrylate oligomer having polyether bonds at both ends can be produced via the diisocyanate compound component by reacting about 2 mol of the diisocyanate compound with respect to 1 mol of the obtained reaction product. When a triisocyanate compound is used instead of the diisocyanate compound, the triisocyanate compound may be added at about 1 mole per 3 moles of the reaction product so that no free isocyanate groups remain. As the diisocyanate compound or triisocyanate compound, a polyisocyanate compound modified with a polyether polyol or polyester polyol containing hydroxyl groups at both ends can also be used.

  When the above-mentioned reactive oligomer (A) is used as an ultraviolet curable resin composition, a photopolymerization initiator (B) is added to this and used.

  Examples of the photopolymerization initiator (B) include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4- Chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoin propyl ether, acetophenone diethyl ketal, benzoin ethyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl Ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy- Examples include 2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and thioxanthone compounds.

  A photoinitiator (B) can be normally mix | blended in the range of about 1-10 weight part with respect to 100 weight of unsaturated compositions.

  In addition to the reactive oligomer (A) and the photopolymerization initiator (B), the composition of the present invention is a polyfunctional unsaturated monomer (C) or colorant for improving film physical properties and adjusting viscosity and reactivity. Can be blended as necessary.

  Examples of the polyfunctional unsaturated monomers (C) include trimethylolpropane triacrylate, bentaerythritol triacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, and 1,4-butanediol diacrylate. 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane trioxyethyl acrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, dicyclopentadiene diacrylate, dicyclo Examples include pentadiacrylate and dicyclopentadiene dimethacrylate.

  Monofunctional unsaturated monomers can also be used to the extent that the coating performance is not degraded. Specifically, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, butoxyethyl acrylate, ethyl diethylene glycol acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenoxyethyl acrylate, dicyclopentadiene acrylate, polyethylene glycol acrylate , Polypropylene glycol acrylate, methyltriethylene diglycol acrylate, isobornyl acrylate, isobornyl methacrylate, N-vinyl pyrrolidone, N-vinyl caprolactam, diacetone acrylamide, isobutoxymethyl acrylamide, N, N-dimethyl acrylamide, t- Octyl acrylamide, dimethylamino ester Le acrylate, diethylaminoethyl acrylate, acryloyl morpholine, dicyclohexylamine Bae integrators sulfonyl acrylate, and dicyclo Bae integrators alkenyl methacrylate.

  In the composition of the present invention, the active energy ray-curable resin composition is applied to the surface of a substrate such as plastic so that the applied amount is 1 to 500 microns in cured film thickness, and then irradiated with active energy rays. It can be carried out by curing. The coating thickness is about 1 to 500 microns, preferably about 3 to 200 microns in terms of cured thickness.

Examples of active energy rays include ultraviolet rays, β rays, and electron beams from mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, carbon arcs, metal halides, gallium lamps, and excimers. Although the irradiation amount of ultraviolet rays is not particularly limited, it is usually preferably in the range of about 10 to 2,000 mj / cm ² . Moreover, in the case of an electron beam, it is preferable that the electron beam of 50-300 KeV is normally irradiated 1-20 Mrad.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, the part of an Example and a comparative example is a basis of weight.

Production Example of Reactive Oligomer A1 Trimethylolpropane 134 g (1 mol), acrylic acid 144 g (2 mol), hydroquinone 500 ppm, P-toluenesulfonic acid 100 ppm, and toluene 276 g were esterified while dehydrating at 110 to 120 ° C. Reaction was performed. When the acid value of the reaction product became 5 KOHmg / g or less, the organic solvent was removed under reduced pressure. Next, 10 mol of ethylene oxide was added, and an addition reaction was carried out to produce a hydroxyl group-containing unsaturated oligomer (a).

  After mixing 2000 g (1 mol) of polypropylene glycol having a molecular weight of 2000 and 444 g (2 mol) of isophorone diisocyanate, the mixture was reacted at 100 ° C. until the isocyanate group became 1/2 to produce a polyisocyanate compound (b).

  Next, 2 mol of the oligomer (a) and 1 mol of the compound (b) are mixed and reacted at 100 ° C. until the isocyanate value becomes 1 or less to obtain a reactive oligomer A1 of 4000 mPa · sec (20 ° C.). It was. This had a number average molecular weight of about 3000 and contained an average of about 4 acryloyl groups in one molecule.

Production Example of Reactive Oligomer A2 Esterification of a blend of 136 g (1 mol) of pentaerythritol, 258 g (3 mol) of methacrylic acid, 500 ppm of methoxyphenol, 100 ppm of P-toluenesulfonic acid and 368 g of toluene at 110 to 120 ° C. Reaction was performed. After the acid value of the reaction product became 5 KOHmg / g or less, the organic solvent was removed under reduced pressure, and then 5 mol of propylene oxide was added, followed by addition reaction to produce a hydroxyl group-containing unsaturated oligomer (c).

  After mixing 2000 g (2 mol) of both-end hydroxyl group polyester resin having a molecular weight of 1000 and 514 g (3 mol) of hexamethylene diisocyanate, the polyisocyanate compound (d) is reacted at 100 ° C. until the isocyanate group becomes 1/3. Manufactured.

  Next, 2 mol of the oligomer (c) and 1 mol of the compound (d) are mixed and reacted at 100 ° C. until the isocyanate value becomes 1 or less to obtain a reactive oligomer A2 of 9000 mPa · sec (20 ° C.). It was. This had a number average molecular weight of about 3200 containing an average of about 6 acryloyl groups in one molecule.

Production Example of Reactive Oligomer A3 A mixture of 222 g (1 mol) of the polyisocyanate compound (b) described above and 232 g (2 mol) of 2-hydroxyethyl acrylate was reacted at 100 ° C. until the isocyanate value became 1 or less. A reactive oligomer A3 of 3000 mPa · sec (20 ° C.) was obtained. This had a number average molecular weight of about 454 containing an average of about 2 acryloyl groups in one molecule.

Example 1
After mixing and mixing 100 g of the reactive oligomer A1 and 3 g of benzoin ethyl ether, the surface of the glass plate was coated to about 100 microns, and then using an 80 W / cm metal halide lamp in a nitrogen atmosphere, Irradiation was performed with an irradiation light amount of 200 mj / cm ² . The gel fraction (* 1) of the cured coating film was 99.2%, the coating film elongation ratio (* 2) was 160%, and the tensile strength (* 3) was 305 kgf / cm ² , which was favorable.

Example 2
A coating film of Example 2 was formed in the same manner as in Example 1 except that the reactive oligomer A2 was used instead of the reactive oligomer A1 in Example 1. As a result, the gel fraction (* 1) of the cured coating film was 99.9%, the coating film elongation ratio (* 2) was 174%, and the tensile strength (* 3) was 246 kgf / cm ² .

Comparative Example 1
A coating film of Example 2 was formed in the same manner as in Example 1 except that the reactive oligomer A3 was used instead of the reactive oligomer A1 in Example 1. As a result, the gel fraction (* 1) of the cured coating film was 95.0%, the coating film elongation ratio (* 2) was 25%, and the tensile strength (* 3) was 200 kgf / cm ² , which was bad.

  Gel fraction (1 *): The coating film is peeled off from a glass plate, placed in a 300 mesh stainless steel mesh container, extracted with a Soxhlet extractor using acetone solvent for 2 hours at reflux temperature, and then according to the following formula: The gel fraction was calculated.

    Gel fraction (%) = (weight after extraction / weight of sample before extraction) × 100

  Elongation rate of coating film (2 *), tensile strength (3 *): Elongation rate and tensile strength of the coating film were measured using Tensilon (“Tensilon UTN II-20”, manufactured by Toyo Baldwin, trade name). A sample having a length of 20 mm and a width of 5 mm was used. The tensile speed was 20 ° C. and 4 mm / min.

Claims (4)

The following general formula (AC) m- (PO)-(R1-O) p-OCHN-
(In the formula, AC represents a (meth) acryloyl group, PO represents a trivalent or higher polyol component residue, m represents m ≦ n−1 when PO uses a polyol component having an n valence, And m is an integer of 2 or 3, R1 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and p represents an integer of 2 to 100.)
An active energy ray-curable non-aqueous resin composition comprising a reactive oligomer (A) having a functional group represented by formula (A) having no salt group . 2. The active energy ray-curable non-aqueous resin composition according to claim 1, wherein in the reactive oligomer (A), the polyol component of the general formula is a 3- to 4-valent polyol component. The reactive oligomer (A) was obtained by reacting a polyol component with (meth) acrylic acid to produce a hydroxyl group-containing polyfunctional (meth) acrylate monomer, and then reacting the hydroxyl group with a monoepoxide. The active energy ray-curable non-aqueous resin composition according to claim 1 or 2, which is obtained by reacting a reaction product with a (polymer) compound containing two or more isocyanate groups until the isocyanate value becomes 1 or less. The ultraviolet curable non-aqueous resin composition according to any one of claims 1 to 3, comprising the reactive oligomer (A) and a photopolymerization initiator (B).