JP2018035264A - Urethane (meth)acrylate, active energy ray-curable resin composition and cured product of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide urethane (meth)acrylate for obtaining a cured product which causes less contamination caused by stickiness by cured with active energy rays.SOLUTION: Urethane (meth)acrylate includes an urethane bond obtained by reaction of a hydroxyl group existing in a polyalkylene oxide and an isocyanate group existing in polyisocyanate, has a mono- or higher functional group (meth)acryloyl group in its terminal, where the polyalkylene oxide satisfies the following (a1) to (a4): (a1) a degree of unsaturation of 0.010 meq/g or less; (a2) a number average molecular weight (M) calculated from the hydroxyl group value of 1,000 or more; (a3) a ratio (Mw/Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) determined by a gel permeation chromatography method of 1.039 or less; and (a4) a number average molecular weight (M) calculated from Mw/Mn and the hydroxyl group value satisfying the following expression (1).SELECTED DRAWING: None

Description

  The present invention relates to urethane (meth) acrylate, an active energy ray-curable resin composition, and a cured product thereof.

  Urethane (meth) acrylates with acryloyl groups at the end are easy to synthesize, and the flexibility, toughness, durability, and weather resistance of the resulting polymers can be changed by changing the type, number, or molecular weight of the functional groups in the urethane moiety. It is a highly versatile (meth) acrylate that can change various physical properties such as water resistance and adhesion. Functional acrylates include, for example, epoxy acrylates, polyester ether acrylates, and silicon acrylates. Compared to these, urethane (meth) acrylates are used in various fields due to their features, and will continue to be used in a wide range of applications in the future. There is expected. In particular, it is a suitable material when rubber elasticity or high elongation is required. In addition, the strong cohesive force due to hydrogen bonding at the urethane bond site and the polymerization rate does not decrease near room temperature, making it an excellent material that can be cured by irradiation with active energy rays such as ultraviolet rays. A cured product of urethane (meth) acrylate is used in various applications. Among these, a cured coating film is one of typical applications, and these coating films are classified into a soft type and a hard type according to the hardness.

  Here, the properties of the soft type coating film change by changing the type and molecular weight of the polyalkylene oxide, polyisocyanate, (meth) acryloyl group-containing isocyanate compound, etc. constituting the urethane moiety of the urethane (meth) acrylate, Depending on the adjustment, a coating film excellent in flexibility, elongation, water resistance and chemical resistance can be obtained, and it is used as an intermediate for an adhesive or paint, or as an ink binder.

  On the other hand, hard type coatings also change the type and molecular weight of polyalkylene oxides, polyisocyanates, (meth) acryloyl group-containing isocyanate compounds, etc. that make up the urethane moiety, and also the number of functional groups on the acryloyl group of urethane (meth) acrylate. As a result, the physical properties change, and after adjustment, the coating film has a high hardness, and is used for the purpose of protecting the surface of plastics and preventing damage to optical films.

  As described above, the physical properties of the coating film obtained by curing urethane (meth) acrylate with active energy rays are greatly influenced by the type of polyalkylene oxide that constitutes the urethane moiety in any of the soft and hard types. By changing the chemical composition and molecular weight of the polyalkylene oxide, the physical properties of the coating film change and the use of the coating film also changes.

  Here, the polyalkylene oxide is generally produced industrially by addition polymerization of alkylene oxide using potassium hydroxide as a catalyst. When polyalkylene oxide is produced by this method, the resulting polyalkylene oxide contains a large amount of monools having one terminal double bond (unsaturated group) as a by-product. When monools with one terminal double bond increase in polyalkylene oxide, the opportunity of reaction between monool and isocyanate compound increases, and urethane with one terminal unsaturated group is produced, but the terminal unsaturated group is an isocyanate compound. As a result, the high molecular weight of the urethane moiety is suppressed, and as a result, when the terminal is an unsaturated group, the reaction is caused by reaction with a hydroxyl group-containing (meth) acrylate or (meth) acryloyl group-containing isocyanate compound. (Meth) acrylate conversion does not progress. Therefore, even if the molecular weight of the polyalkylene oxide is selected in order to obtain a cured product that satisfies the intended physical properties, if a polyalkylene oxide containing a large amount of monools at one terminal double bonds (unsaturated groups) is used, urethane The molecular weight of the site is insufficient, resulting in urethane (meth) acrylate in which some acryloyl groups are not introduced at the ends, and even if they are cured with active energy rays, the cured product exhibits the intended physical properties. I can't.

  Furthermore, since some of the ends of urethane (meth) acrylate are stopped by unreactive double bonds (unsaturated groups), the cured product obtained by curing urethane (meth) acrylate with active energy rays is involved in crosslinking. Molecular chains are not present, the stickiness of the cured product becomes remarkable, the surrounding dust and dust adhere to the cured product over time, and the cured product is contaminated. Needless to say, the functions required of the cured product, such as transparency, are deteriorated with time, and cannot withstand long-term use.

  Therefore, in order to cure urethane (meth) acrylate using polyalkylene oxide with active energy rays to obtain a non-sticky cured product having the intended physical properties, one end double bond (unsaturated group) in polyalkylene oxide is obtained. ) Monool is extremely important. In addition, since monool has a low molecular weight, if the monool in the polyalkylene oxide is reduced, the low molecular weight component in the polyalkylene oxide is also reduced.

  As polyalkylene oxides having a small monool, polyalkylene oxides obtained by using a double metal cyanide complex as a catalyst are known (for example, see Patent Documents 1 and 2). However, the polyalkylene oxides described in Patent Documents 1 and 2 have a wide molecular weight distribution, and the catalysts described in Patent Documents 1 and 2 also have a problem that ethylene oxide, which is frequently used in the field as an alkylene oxide, is difficult to adapt. .

  Moreover, as polyalkylene oxide with few monools, polyalkylene oxide obtained by using a specific phosphazenium salt as a catalyst is known (see, for example, Patent Documents 3, 4, and 5). However, the polyalkylene oxides described in Patent Documents 3, 4, and 5 are still many monools.

  Furthermore, polyalkylene oxides obtained using a catalyst comprising a phosphazene compound and triisobutylaluminum are also known as polyalkylene oxides having a small monool (see, for example, Non-Patent Document 1). However, the polyalkylene oxide described in Non-Patent Document 1 has a broad molecular weight distribution.

  Here, when trying to obtain urethane (meth) acrylate using polyalkylene oxide with few monools but wide molecular weight distribution, the molecular weight distribution of urethane (meth) acrylate also widens, leading to handling problems due to high viscosity. Or the cured structure obtained by irradiating these urethane (meth) acrylates with active energy rays has a non-uniform cross-linking structure (uneven molecular weight between cross-linking points), making it difficult for the cured product to exhibit stable physical properties. .

US Pat. No. 5,235,114 Japanese Patent Laid-Open No. 4-59825 Japanese Patent No. 3497004 (Japanese Patent Laid-Open No. 10-77289) Japanese Patent No. 3905638 (Japanese Patent Laid-Open No. 11-106500) Japanese Patent No. 5663856 (Japanese Patent Laid-Open No. 2010-150514)

Polymer Chemistry, 2012, 3, 1189.

  The present invention has been made in view of the above-mentioned background art, and its purpose is to easily express the intended physical properties in a cured product obtained by curing urethane (meth) acrylate with active energy rays. An object of the present invention is to provide a urethane (meth) acrylate for obtaining a cured product that is less contaminated by stickiness.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an active energy ray-curable resin composition containing a specific urethane (meth) acrylate solves the above-mentioned problems and completed the present invention. It came to do.

  That is, the present invention includes the following embodiments.

  [1] It contains a urethane bond obtained by reacting a hydroxyl group present in the polyalkylene oxide (A) with an isocyanate group present in the polyisocyanate (B), and has at least one (meth) acryloyl group having at least one functional group. A urethane (meth) acrylate having a group and the polyalkylene oxide (A) satisfies all of the following (a1) to (a4).

  (A1) The degree of unsaturation is 0.010 meq / g or less.

  (A2) The number average molecular weight calculated from the hydroxyl value (OHV) is 1000 or more.

  (A3) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) using polystyrene as a standard substance is 1.039 or less.

  (A4) The number average molecular weight (M) calculated from Mw / Mn and hydroxyl value (OHV) determined by gel permeation chromatography (GPC) using polystyrene as a standard substance is expressed by the following formula (1). Fulfill.

  [2] Using polystyrene as a standard substance, Mw / Mn of polyalkylene oxide (A) determined by the GPC method was connected in series to four columns filled with a 3 μm particle size filler in a separation column, and the reference side The urethane (meth) acrylate according to [1] above, which is a molecular weight distribution analyzed under conditions using a resistance tube connected and tetrahydrofuran as a developing solvent.

  [3] The above, wherein the polyalkylene oxide (A) is obtained by ring-opening polymerization of alkylene oxide using a catalyst in which an imino group-containing phosphazenium salt and a Lewis acid are used in combination. The urethane (meth) acrylate according to [1] or [2].

  [4] Isocyanate group (NCO group) -containing urethane prepolymer (C) obtained by reacting polyalkylene oxide (A) and polyisocyanate (B), and hydroxyl group-containing (meta) having one or more acryloyl groups ) A process for producing a urethane (meth) acrylate according to any one of the above [1] to [3], wherein the acrylate (D) is reacted.

  [5] Polyisocyanate (B) is polymethylene polyphenylene polyisocyanate (polymeric MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane Diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, pentamethylene diisocyanate, 1,6-hexamethylene In the above [4], which is at least one selected from the group consisting of diisocyanates, these isocyanate-containing prepolymers, and modified products of these isocyanates Manufacturing method of the mounting.

  [6] The above [1] to [3], wherein the polyalkylene oxide (A) is reacted with a (meth) acryloyl group-containing isocyanate compound (E) having one or more (meth) acryloyl groups. ] The manufacturing method of the urethane (meth) acrylate in any one of.

  [7] An active energy ray-curable resin composition comprising the urethane (meth) acrylate according to any one of [1] to [3] above and a photopolymerization initiator.

  [8] A cured product of the active energy ray-curable resin composition according to [7].

  [9] A cured coating film of the active energy ray-curable resin composition according to [7].

  The active energy ray-curable resin composition containing the urethane (meth) acrylate of the present invention and a photopolymerization initiator is easy to stretch after being charged into the mold and has good workability. Moreover, by curing the active energy ray-curable resin composition with active energy rays, cured products that are less contaminated by stickiness and easily express the intended physical properties can be obtained. As a representative, it can be suitably used for various applications.

  The urethane (meth) acrylate of the present invention contains a urethane bond obtained by reacting a hydroxyl group present in the polyalkylene oxide (A) with an isocyanate group present in the polyisocyanate (B), and has one functional group at the end. It is characterized by having at least a (meth) acryloyl group and that the polyalkylene oxide (A) satisfies all of the following (a1) to (a4).

  (A1) The degree of unsaturation is 0.010 meq / g or less.

  (A2) The number average molecular weight calculated from the hydroxyl value (OHV) is 1000 or more.

  (A3) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) using polystyrene as a standard substance is 1.039 or less.

  (A4) The number average molecular weight (M) calculated from Mw / Mn and hydroxyl value (OHV) determined by gel permeation chromatography (GPC) using polystyrene as a standard substance is the above formula (1). Fulfill.

In the present invention, the polyalkylene oxide (A) is not particularly limited. For example, as a bifunctional polyalkylene oxide, one or more active hydrogen compounds R [—H] _m are used, and one or more three-membered alkylene oxides having 2 to 12 carbon atoms are added. The alkylene oxide adduct is preferably a polyalkylene oxide represented by the following general formula (1).

[In general formula (1), R is an m-valent group obtained by removing m active hydrogens from an active hydrogen-containing compound (R [—H] _m ), Z is an alkylene group or cycloalkylene having 2 to 12 carbon atoms. And A is an alkylene group having 3 carbon atoms. When there are a plurality of Z or A, each may be the same or different. m is 2, p is 0 or an integer of 1 to 500, q is an integer of 1 to 1000, and r is 0 or an integer of 1 to 500. ]
In the present invention, a compound having an oxyalkylene group and having at least two active hydrogen groups per molecule in an arbitrary position such as a polymer terminal or a branched chain terminal is preferable.

Here, the active hydrogen-containing compound (R [—H] _m ) is not particularly limited as long as it has an active hydrogen group. For example, bifunctional diols such as water, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, tripropylene glycol, triethylene glycol, polyoxyalkylene diol, bisphenol A, bisphenol Examples thereof include compounds having two active hydrogen groups such as F, bisphenols such as bisphenol AD, dihydroxybenzenes such as catechol, resorcin, and hydroquinone, and amines such as methylamine, ethylamine, propylamine, and butylamine. As the active hydrogen-containing compound (R [—H] _m ), one or a mixture of two or more selected from these can be used.

The alkylene oxide added to the active hydrogen-containing compound (R [—H] _m ) is not particularly limited as long as it is a compound having one or more epoxy rings in the molecule. Examples thereof include alkylene oxides having 2 to 12 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. As the alkylene oxide, one or a mixture of two or more selected from these may be used.

  Of these, one or two or more alkylene oxides containing an alkylene oxide having 2 to 3 carbon atoms such as propylene oxide and ethylene oxide, which are easily available industrially, are preferred, and one or two kinds containing propylene oxide are preferred. The above alkylene oxide is more preferable.

  ZO in the general formula (1) is a polyether derived from an alkylene oxide having 2 to 12 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc., because the viscosity tends to be low and good urethane moldability is exhibited. It preferably has a structure. More preferred is a polyether structure derived from one or more alkylene oxides selected from ethylene oxide and propylene oxide, and most preferred is one polyether structure selected from ethylene oxide and propylene oxide.

  P in the general formula (1) is 0 or an integer of 1 to 500, preferably p = 0 or an integer of 1 to 100, and more preferably p = 0.

  Examples of Z in the general formula (1) include a structure represented by the following general formula (2).

[In General Formula (2), R _{2 to} R ₅ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. However, the total carbon number of R _{2 to} R ₅ does not exceed 10. Further, any _two of R _{2 to} R ₅ may be bonded to form a cycloalkyl group. ]
In addition, the AO in the general formula (1) is a polyether structure derived from an alkylene oxide having 3 carbon atoms such as propylene oxide because the viscosity tends to be low and the polyurethane elastomer is likely to exhibit good mechanical properties. It is preferable that

  As A in the said General formula (1), the structure shown by following formula (3) is mentioned, for example.

  Q in the said General formula (1) is an integer of 1-1000, Preferably it is an integer of q = 10-500, More preferably, it is an integer of q = 15-250.

  R in the general formula (1) is 0 or an integer of 1 to 500. Since it is difficult to solidify at low temperature and easy to handle, it is preferably r = 0 or an integer of 1-90, more preferably r = 0.

  As the relationship between p, q and r in the general formula (1), the viscosity tends to be low, and good mechanical properties are easily obtained when urethane is used. Therefore, p + q> r (where p + q is 10 to 1000, It is preferable that q is 10 to 1000 and r is 0 or 1 to 90). More preferably, p + q> 5r (where p + q is 30 to 600, q is 30 to 500, r is 0 or 1 to 90), and most preferably p + q> 10r (where p + q is 50 to 600, q 50 to 500 and r is 0 or 1 to 90).

In addition, when a trifunctional polyalkylene oxide is used as the polyalkylene oxide (A) in the present invention, for example, one or more active hydrogen compounds R [—H] _m are used, and the number of carbon atoms is 2 to 12. An alkylene oxide adduct obtained by adding one or more of the three-membered alkylene oxide is preferable, and a polyalkylene oxide represented by the following general formula (4) is preferable.

[In General Formula (4), R is an m-valent group obtained by removing m active hydrogens from an active hydrogen-containing compound (R [—H] _m ), Z is an alkylene group or cycloalkylene having 2 to 12 carbon atoms. And A is an alkylene group having 3 carbon atoms. When there are a plurality of Z or A, each may be the same or different. m is an integer of 3 to 100, p is 0 or an integer of 1 to 500, q is an integer of 1 to 1000, and r is 0 or an integer of 1 to 500. ]
Here, the active hydrogen-containing compound (R [—H] _m ) is not particularly limited as long as it has an active hydrogen group, and examples thereof include those described above.

The alkylene oxide added to the active hydrogen-containing compound (R [—H] _m ) is not particularly limited as long as it is a compound having one or more epoxy rings in the molecule. For example, C2-C12 alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, are mentioned, You may use 1 type, or 2 or more types of alkylene oxide.

  Of these, one or two or more alkylene oxides containing an alkylene oxide having 2 to 3 carbon atoms such as propylene oxide and ethylene oxide, which are easily available industrially, are preferred, and one or two kinds containing propylene oxide are preferred. The above alkylene oxide is more preferable. Although m in the said General formula (4) will not be specifically limited if it is the range of 3-100, It is preferable that it is the range of 3-5.

  As the polyalkylene oxide (A) used in the present invention, the molecular weight distribution is likely to be narrow and the handling property is easily improved. Therefore, the diol of the general formula (1) and the triol of m = 3 in the general formula (4) Are preferably used in combination.

  When two or more kinds of polyalkylene oxides are used in combination, it is more preferable that each has the above structure, but it can be suitably used if the molecular structure of the polyalkylene oxide having a higher content weight has the above structure.

  The degree of unsaturation of the polyalkylene oxide (A) used in the present invention is 0.010 meq / g or less. Preferably, it is the range of 0.002-0.009 meq / g, More preferably, it is the range of 0.004-0.008 meq / g.

  When a polyalkylene oxide having a high degree of unsaturation exceeding 0.010 meq / g is used, the polyalkylene oxide contains a large amount of monools having one terminal double bond (unsaturated group). If the monool with one terminal double bond increases in the polyalkylene oxide, the opportunity for the reaction between the monool and the isocyanate compound increases and a urethane with one terminal unsaturated group is produced. Does not react, and as a result, high molecular weight of the urethane moiety is suppressed.

  In addition, when the terminal is an unsaturated group, (meth) acrylate formation by reaction with a hydroxyl group-containing (meth) acrylate or (meth) acryloyl group-containing isocyanate compound does not proceed. Therefore, even if the molecular weight of the polyalkylene oxide is selected in order to obtain a cured product that satisfies the intended physical properties, if a polyalkylene oxide containing a large amount of monools at one terminal double bonds (unsaturated groups) is used, urethane The molecular weight of the site is insufficient, resulting in urethane (meth) acrylate in which some acryloyl groups are not introduced at the ends, and even if they are cured with active energy rays, the cured product exhibits the intended physical properties. I can't.

  Furthermore, since some of the ends of urethane (meth) acrylate are stopped by unreactive double bonds (unsaturated groups), the cured product obtained by curing urethane (meth) acrylate with active energy rays is involved in crosslinking. Molecular chains are not present, the stickiness of the cured product becomes remarkable, the surrounding dust and dust adhere to the cured product over time, and the cured product is contaminated. Needless to say, the functions required of the cured product, such as transparency, are deteriorated with time, and cannot withstand long-term use.

  In the present invention, the degree of unsaturation (meq / g) of the polyalkylene oxide (A) is the total amount of unsaturated groups contained in 1 g of the polyalkylene oxide (A), and is defined in JIS K1557 6.7. It is a value measured according to the method.

  The polyalkylene oxide (A) used in the present invention is a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) using polystyrene as a standard substance (Mw / Mn). ) Is 1.039 or less, preferably in the range of 1.003 to 1.029, more preferably in the range of 1.005 to 1.019, and most preferably in the range of 1.006 to 1.016. It is.

  When this Mw / Mn exceeds 1.039, the viscosity of the polyalkylene oxide (A) is increased due to the increase in the high molecular weight component, and the urethane (meth) acrylate and the photopolymerization initiator obtained thereby are used. When using the active energy ray resin composition containing as a coating film, the coating property to a base material and the uniformity of a coating film are inferior.

  The polyalkylene oxide (A) used in the present invention is a number average molecular weight (calculated from Mw / Mn and hydroxyl value (OHV) described later by gel permeation chromatography (GPC) using polystyrene as a standard substance ( M) satisfies the above formula (1). It is preferably satisfying the following formula (2), and more preferably satisfying the following formula (3).

  Mw / Mn obtained by GPC method using polystyrene as a standard substance, for reasons described later, four columns filled with a 3 μm particle size filler are connected in series to a separation column, and a resistance tube is connected to the reference side. The molecular weight distribution is preferably measured and analyzed under conditions using tetrahydrofuran as a solvent, and is preferably Mw / Mn calculated using a cubic approximate curve calibration curve using standard polystyrene.

  The number of separation columns is preferably 3 to 5 because the resolution (theoretical plate number) is high and it is easy to suppress the spread of the molecular weight due to fluctuations in the baseline and minute peaks of impurities in the liquid. Preferably four.

  The particle size of the packing material in the separation column is preferably 1 to 4.5 μm because the measurement time is appropriate and it is easy to suppress the spread of molecular weight due to fluctuations in the baseline and minute peaks of impurities in the liquid. Particularly preferably, it is 3 μm.

  The exclusion limit of the separation column is preferably 50,000 to 3 million, more preferably 60,000 to 400,000. The inner diameter of the separation column is preferably 5 to 7.5 mmφ, more preferably 6 mmφ. The length of the separation column is preferably 10 to 25 cm, more preferably 15 cm.

  Examples of such a separation column include Tskel SuperH4000 and Tskel SuperH3000 manufactured by Tosoh Corporation. The most preferable configuration of the separation column is a configuration in which a total of four Tskel SuperH4000 × 2 and Tskel SuperH3000 × 2 manufactured by Tosoh Corporation are connected in series.

  The flow rate on the separation column side is preferably 0.5 to 0.9 ml / min, more preferably 0.6 ml / min. The column temperature is preferably 30 ° C to 50 ° C, more preferably 40 ° C.

  In addition, it is preferable to connect 2 to 6 resistance tubes, more preferably 5 resistance tubes, and most preferably, since it is easy to suppress the molecular weight distribution from spreading due to pump pulsation on the reference side. Is a connection of five resistance tubes and one separation column.

  As the resistance tube, a tube having a length of 2 m and an inner diameter of 0.1 mmφ is preferable.

  The flow rate on the reference side is preferably 0.1 to 0 in the state of five resistance tubes because the pump pulsation cycle is short and it is easy to suppress fluctuations in the baseline, and it is easy to suppress the molecular weight distribution from spreading due to the pump pulsation. 0.6 ml / min, more preferably 0.15 ml / min.

  The polystyrene used for the standard material of the cubic approximate curve calibration curve is preferably 6 to 10 points, more preferably 8 points. The molecular weight of polystyrene used for the standard substance having a known molecular weight is preferably selected from the range of 300 to 3000000, and more preferably selected from the range of 450 to 1100000. Specifically, for example, eight-point selection of 500, 1010, 2630, 10200, 37900, 96400, 427000, 1090000, and the like, and the measurement of the standard substance are 4 points of 500, 2630, 37900, 427000 and 1010, 10200, The measurement may be performed in two steps, such as 4 points of 96400 and 1090000.

  The developing solvent is preferably dimethylformamide or tetrahydrofuran, and more preferably BHT stabilizer-containing special grade tetrahydrofuran manufactured by Wako Pure Chemical Industries.

The sample concentration is preferably 0.5 to 2 mg / ml, more preferably 1 mg / ml. The injection amount of the sample solution is preferably 10 to 90 μl, more preferably 20 μl, in which the peak is difficult to broaden and the molecular weight distribution is difficult to spread.
Here, the number average molecular weight (M) calculated from the OHV of the polyalkylene oxide (A) is based on the hydroxyl value (OHV, the unit is mgKOH / g) of the polyalkylene oxide (A). ).

  OHV is a value measured according to JIS K1557 6.4, and the number of hydroxyl groups per molecule is an active hydrogen compound 1 which is an initiator used as a raw material when producing polyalkylene oxide (A). The number of active hydrogen atoms per molecule. If the number of active hydrogen atoms in the initiator cannot be determined with a commercial product, the nominal number of functional groups is used.

  In the present invention, the number average molecular weight (M) calculated from the OHV of the polyalkylene oxide (A) is 1000 or more. Preferably it is the range of 2000-30000, More preferably, it is the range of 4000-30000.

  The polyalkylene oxide (A) in the present invention is liquid at room temperature and is preferably an amorphous compound. If it is liquid at room temperature, it can be used without heating and is easy to handle.

  In addition, for the polyalkylene oxide (A) in the present invention, the area ratio of the low molecular weight component in the GPC method is preferably 4.5% or less, preferably 2% or less, based on polystyrene as a standard substance. More preferably. This is obtained when cured with active energy rays by using an active energy ray resin composition containing urethane (meth) acrylate obtained from polyalkylene oxide (A) satisfying this requirement and a photopolymerization initiator. This is because the stickiness of the cured product is further reduced.

  Here, the “low molecular weight component” in the GPC method refers to a component having a molecular weight corresponding to a number average molecular weight of 1/3 or less of the number average molecular weight (Mn) calculated by the GPC method using polystyrene as a standard substance. The area ratio corresponds to the ratio of the area surrounded by the baseline and the baseline corresponding to the “low molecular weight component” to the area surrounded by the GPC baseline and all peak curves. .

  Moreover, in this invention, the glass transition temperature of polyalkylene oxide (A) hardens | cures the active energy ray resin composition containing the urethane (meth) acrylate obtained using it, and a photoinitiator with an active energy ray. Since the brittleness in the low temperature environment of the hardened | cured material obtained by this can be improved, it is preferable that it is -30 degrees C or less.

  In the present invention, the viscosity of the polyalkylene oxide (A) at 25 ° C. is not particularly limited and is appropriately selected depending on the application. However, it is preferably in the range of 0.1 to 2000 Pa · s, more preferably in the range of 0.2 to 200 Pa · s. If the viscosity of the polyalkylene oxide (A) is in the range of 0.1 to 2000 Pa · s, an active energy ray-curable resin composition containing a urethane (meth) acrylate obtained from the polyalkylene oxide (A) and a photopolymerization initiator is handled. For example, when the resin composition is used as a coating film, the coating property of the resin composition to the base material is improved.

  In the present invention, the viscosity at 25 ° C. refers to a value measured with a cone plate rotational viscometer described in JIS K1557-5 6.2.3. Specifically, it refers to the viscosity at a shear rate of 0.1 (1 / s), but when the viscosity does not fall within the measurement range, the shear rate range is set to 0.01 to 10 (1 / s to enter the measurement range. ) May be adjusted within the range.

  In the present invention, the production method of the polyalkylene oxide (A) is not particularly limited. For example, ring-opening polymerization of alkylene oxide is performed in the presence of an active hydrogen-containing compound, a base catalyst, and a Lewis acid. Can be manufactured.

  For example, when active hydrogen-containing compounds and a base catalyst are mixed and treated under reduced pressure to sufficiently prepare a catalytically active species precursor, water and solvent are sufficiently removed, and further Lewis acid is mixed and treated under reduced pressure for catalytic activity. Suppressing the polyalkylene oxide derived from Lewis acid, which is a factor that broadens the molecular weight distribution by sufficiently removing by-products when adjusting the species and selecting a specific Lewis acid that is a by-product with a low boiling point, It is preferable to produce by a production process in which alkylene oxide is added using a catalyst in which a base catalyst with few side reactions and a specific Lewis acid are combined, an alkylene oxide having a moisture value of 100 ppm or less, and the like. However, it is not particularly limited.

  The base catalyst is not particularly limited, but it is preferable to use a catalyst system in which a base catalyst and a Lewis acid are used in combination because the alkylene oxide has a wide application range, a high polymerization activity, and a low degree of unsaturation. .

  Here, the Lewis acid is not particularly limited, and examples thereof include an aluminum compound, a zinc compound, and a boron compound. Of these, organoaluminum, aluminoxane, and organozinc are preferable, and organoaluminum is more preferable because it becomes an alkylene oxide polymerization catalyst having excellent catalytic performance.

  Examples of the aluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trinormalhexylaluminum, triethoxyaluminum, triisopropoxyaluminum, triisobutoxyaluminum, triphenylaluminum, diphenylmonoisobutylaluminum, monophenyldiisobutylaluminum, etc. Organic aluminum; an aluminoxane such as methylaluminoxane, isobutylaluminoxane, and methyl-isobutylaluminoxane; and inorganic aluminum such as aluminum chloride, aluminum hydroxide, and aluminum oxide.

  Among these, trimethylaluminum, triethylaluminum, which are easy to remove because the boiling point of by-products during the preparation of the catalytically active species is as low as 100 ° C. or less, and are easy to suppress the polyalkylene oxide derived from Lewis acid, which causes the molecular weight distribution to be broadened. Triisobutyl aluminum, trinormal hexyl aluminum, triethoxy aluminum, triisopropoxy aluminum and the like are preferable. The compound produced as a by-product in the preparation of the catalytically active species can be judged from the structure of Lewis acid. For example, trimethylaluminum has H added to the methyl group of the substituent on aluminum, and triisobutylaluminum has the isobutyl substituent on aluminum. In the case of isobutane in which H is added to the group, triisopropoxyaluminum is isopropanol in which H is added to the isopropoxy group.

  Examples of the zinc compound include organic zinc such as dimethyl zinc, diethyl zinc and diphenyl zinc; and inorganic zinc such as zinc chloride and zinc oxide.

  Examples of the boron compound include triethylborane, trimethoxyborane, triethoxyborane, triisopropoxyborane, triphenylborane, tris (pentafluorophenyl) borane, and trifluoroborane.

  The base catalyst is not particularly limited, but a basic compound having a PN bond is desirable. More preferably, it is a base compound having an imino group and a PN bond, and examples thereof include an iminophosphazenium salt compound represented by the following general formula (5) (for example, see JP 2011-132179 A). .

[In General Formula (5), R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Incidentally, the R ₁ and R ₂ may be bonded to form a ring structure, R ₁ s or R ₂ together may form a ring structure together. X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion. ]
The ratio of the base catalyst to the Lewis acid is not particularly limited, and may be arbitrary as long as the action as an alkylene oxide polymerization catalyst is expressed. For example, the base catalyst: Lewis acid = 1: 0.002-500 (mol) Ratio).

  In the present invention, the polymerization temperature at the time of producing the polyalkylene oxide (A) is not particularly limited. However, since the polyalkylene oxide (A) is decomposed and the molecular weight distribution is hardly widened and the catalytic activity is easily exhibited. The range of -150 degreeC is preferable, More preferably, it is the range of 90-110 degreeC.

  The polymerization pressure for producing the polyalkylene oxide (A) is not particularly limited, but is in the range of 0.05 to 1.0 MPa, preferably in the range of 0.1 to 0.6 MPa.

  Further, the stirring speed at the time of producing the polyalkylene oxide (A) is not particularly limited, and depends on the shape and inner volume of the polymerization vessel, the shape of the stirring blade, etc. In the case of a stirring blade, it is preferable to sufficiently stir at 300 rpm or more.

  When an alkylene oxide is added to an active hydrogen-containing compound using a catalyst in which an iminophosphazenium salt and a Lewis acid are combined, the iminophosphazenium salt (including its precursor), Lewis acid, and active hydrogen-containing compound Are mixed simultaneously and heated / depressurized to prepare a catalytically active species, and one of these components is mixed with two other components and heated / depressurized to prepare a catalytically active species. , A method of preparing a catalytically active species by mixing two other components with one of these and performing heating / depressurization treatment, etc., and mixing two of these components with heating / depressurizing treatment etc. to perform catalytic activity After preparing the seed precursor, any other method may be used, such as a method of preparing a catalytically active species by mixing other one component and further performing heating / depressurization treatment. Of these, since by-products and impurities are easily removed and polyalkylene oxide (A) having a narrow molecular weight distribution is easily obtained, it is preferable to mix an iminophosphazenium salt and an active hydrogen-containing compound, followed by heating and decompression treatment. After that, it is preferable to go through a production process in which a Lewis acid is mixed, followed by heating / depressurizing treatment, etc. to prepare a catalytically active species and add an alkylene oxide.

  In this case, the temperature of the heating / depressurizing treatment is preferably 100 ° C. or more, more preferably in the range of 100 to 130 ° C., because by-products and impurities are easily removed and polyalkylene oxide (A) having a narrow molecular weight distribution is easily obtained. It is. The pressure during the heating / depressurization treatment is preferably less than 0.5 kPa, more preferably 0.001 to 0, because by-products and impurities are easily removed and polyalkylene oxide (A) having a narrow molecular weight distribution is easily obtained. The range is 2 kPa. The heating / depressurization time in this case is 2 hours or more after mixing the iminophosphazenium salt (including its precursor), Lewis acid, and active hydrogen-containing compound, although it varies depending on the shape of the reaction vessel. More preferably, the iminophosphazenium salt (including its precursor) and the active hydrogen-containing compound are mixed for 2 hours or more after heating and vacuum distillation, and after mixing with Lewis acid, further heating and vacuum distillation. It is preferable to carry out the last two hours or more. Further, a low-boiling dehydrated solvent may be added to remove impurities, and azeotropic operation may be performed to remove impurities.

  In the present invention, the amount of catalyst residue in the polyalkylene oxide (A) is not particularly limited. However, since the viscosity may increase when the catalyst remains, it is preferable to remove the catalyst after polymerization. . The amount of catalyst residue in the polyalkylene oxide (A) is preferably 200 ppm or less, and more preferably 100 ppm or less. Here, as the catalyst residue amount, when two or more types of catalysts are used in combination, the catalyst residue amount is the sum of catalyst residues.

  Next, the manufacturing method of the urethane (meth) acrylate of this invention is demonstrated.

  Although it does not specifically limit as a manufacturing method of the urethane (meth) acrylate of this invention, For example, the isocyanate group (NCO group) containing urethane obtained by making polyalkylene oxide (A) and polyisocyanate (B) react. It is preferable to obtain the prepolymer (C) by reacting with a hydroxyl group-containing (meth) acrylate (D) having one or more acryloyl groups.

  The polyisocyanate (B) is not particularly limited, and examples thereof include compounds having at least two isocyanate groups.

  Specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1 , 4-cyclohexane diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatome) L) Cyclohexane, pentamethylene diisocyanate, norbornane diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicyclo Examples include heptane triisocyanate, trimethylhexamethylene diisocyanate, an isocyanate-containing prepolymer obtained by reacting them with a polyol, and a mixture of two or more thereof. Furthermore, modified products of these isocyanates (for example, modified products containing urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, isocyanurate groups, amide groups, imide groups, uretonimine groups, uretdione groups or oxazolidone groups), Condensates such as polymethylene polyphenylene polyisocyanate (polymeric MDI) (sometimes referred to as polynuclear) are also included.

  Among these, since the reactivity of polyalkylene oxide (A) is excellent and it is easy to obtain an isocyanate group (NCO group) -containing urethane prepolymer (C), polymethylene polyphenylene polyisocyanate (polymeric MDI), 2,4-tri- Diisocyanate, 2,6-tolylene diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, 1,4-bis (isocyanatomethyl) ) Cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, pentamethylene diisocyanate, these isocyanate group-containing prepolymers, modified products of these isocyanates (for example, Urethane group, carbodiimide group, allophanate group, urea group, biuret group, isocyanurate group, amide group, imide group, uretonimine, uretdione or oxazolidone group-containing modified products) and the like are preferable. Further, since the flexibility of the cured product when urethane acrylate is cured with ultraviolet rays is excellent, 1,6-hexamethylene diisocyanate, modified products of these isocyanates (for example, urethane group, carbodiimide group, allophanate group, urea group, A burette group, isocyanurate group, amide group, imide group, uretonimine group, uretdione group or oxazolidone group-containing modified product) can be preferably used. These isocyanates may be used alone or in combination.

  Although it does not specifically limit as a functional group number (the number of NCO functional groups in 1 molecule) of polyisocyanate (B), It is preferable that it is 2-6 functionality, More preferably, it is 2-3 functionality.

  The polyisocyanate (B) is added in a molar ratio (NCO / OH mol) between the total amount of NCO groups in the polyisocyanate (B) and the total amount of OH groups in the active hydrogen-containing compound such as the polyalkylene oxide (A). Ratio and description) is preferably in the range of an addition amount of 0.30 to 5.00. More preferably, the NCO / OH molar ratio is in the range of 1.00 to 3.00.

  When the ratio of the total amount of NCO groups in the polyisocyanate (B) to the total amount of OH groups in the active hydrogen-containing compound is less than 0.30, the viscosity of the isocyanate group (NCO group) -containing urethane prepolymer (C) increases, When urethane (meth) acrylate is obtained by reaction with the contained (meth) acrylate (D), the handling is hindered.

  The amount of polyisocyanate (B) added is not particularly limited, but is preferably in the range of 0.5 to less than 200 parts by weight, more preferably 5 to 70 parts per 100 parts by weight of polyalkylene oxide (A). Less than parts by weight, most preferably in the range of less than 10 to 50 parts by weight.

  Here, the isocyanate group (NCO group) -containing urethane prepolymer (C) is obtained by reacting a polyalkylene oxide (A) and a polyisocyanate (B), and has two or more NCO groups at its ends. Examples of the properties include liquid compounds.

  The viscosity of the isocyanate group (NCO group) -containing urethane prepolymer (C) used in the present invention is not particularly limited, but when the urethane (meth) acrylate is obtained by reacting with the hydroxyl group-containing (meth) acrylate (D), the urethane ( Work to obtain an active energy ray-curable resin composition by adding a photopolymerization initiator to (meth) acrylate, and to cure the active energy ray-curable resin composition by irradiation with active energy rays to obtain a cured product The viscosity at 25 ° C. is 1000 to 200000 mPa.s. It is preferable that it is the range of s, More preferably, it is the range of 3000-100000 mPa * s.

  The number average molecular weight in terms of standard polystyrene of the isocyanate group (NCO group) -containing urethane prepolymer (C) used in the present invention is not particularly limited. However, since workability is good at an appropriate viscosity, it is 1000 to 100,000. A range is preferable. More preferably, it is the range of 1000-40000. The number average molecular weight in terms of standard polystyrene is measured by GPC (gel permeation chromatography) under the conditions of a column temperature of 40 ° C., a flow rate of 1.0 ml / min, and a solvent THF, and a cubic approximate curve calibration curve using standard polystyrene. Can be calculated as

  The method for synthesizing the isocyanate group (NCO group) -containing urethane prepolymer (C) used in the present invention is not particularly limited. For example, the polyalkylene oxide (A) and the polyisocyanate (B) described above, if necessary, Examples thereof include a method in which other active hydrogen-containing compounds are subjected to a urethanization reaction in the presence of a urethanization catalyst, a solvent, an antifoaming agent, other additives, and the like. Therefore, the obtained active energy ray-curable resin composition containing an isocyanate group (NCO group) -containing urethane prepolymer (C), a urethane (meth) acrylate obtained therefrom, and a photopolymerization initiator is urethanized. A catalyst, an antifoaming agent, an additive, etc. may be included.

  Although it does not specifically limit as reaction temperature at the time of synthesize | combining an isocyanate group (NCO group) containing urethane prepolymer (C), It is preferable that it is the range of 50 to 130 degreeC.

  Here, as the urethanization catalyst, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, organotin compounds such as tin 2-ethylhexanoate, iron compounds such as iron acetylacetonate and iron chloride, octylic acid Lead compounds such as lead, bismuth compounds such as bismuth octylate, tertiary amine catalysts such as triethylamine and triethylenediamine, and the like, preferably one or more selected from organic tin compounds, lead octylate and bismuth octylate A catalyst is preferred.

  The hydroxyl group-containing (meth) acrylate (D) having at least one acryloyl group used in the present invention is not particularly limited, but in the case of monofunctional or bifunctional, for example, 2-hydroxyethyl acrylate, 2 -Hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, polyethylene glycol monoacrylate, acryloylmorpholine, isobornyl acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated water Examples thereof include bisphenol A diacrylate, ethoxylated cyclohexanedimethanol diacrylate, and tricyclodecane dimethanol diacrylate. In the case of trifunctional, tetrafunctional or pentafunctional, for example, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol (meth) tetraacrylate, dipentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, sold by Daicel Cytec EBECRYL 264, EBECRYL 8210, EBECRYL 8405, U-4HA sold by Shin-Nakamura Chemical Co., Ltd. It is. As the hydroxyl group-containing (meth) acrylate (D) having one or more functional groups, two or more of these may be used in combination.

  In the present invention, it is preferable not to use a hydroxyl group-containing (meth) acrylate (D) that contains a hexafunctional or higher functional acryloyl group. When the acryloyl group has 6 or more functional groups, the hardness of the cured product obtained by curing the active energy ray resin composition containing the urethane (meth) acrylate and the photopolymerization initiator obtained with the active energy ray becomes excessively high. Although it is advantageous in terms of scratch resistance for objects, it may be inferior in impact resistance.

  When reacting the isocyanate group in the isocyanate group (NCO group) -containing urethane prepolymer (C) with the hydroxyl group in the hydroxyl group-containing (meth) acrylate (D) having one or more acryloyl groups, an isocyanate group (NCO group) ) -Containing urethane prepolymer (C) and the mixing ratio of the hydroxyl group-containing (meth) acrylate (D): 0.5 ≦ [number of hydroxyl group equivalents of (D) / number of isocyanate group equivalents of (C)] ≦ 5.0 It is preferable to carry out in a temperature range of 30 to 90 ° C. so that 0.8 ≦ [number of hydroxyl group equivalents of (D) / number of isocyanate group equivalents of (C)] ≦ 3.0 and 60 to 80 More preferably, it is carried out in the temperature range of ° C.

  In the present invention, the number of hydroxyl group equivalents and the number of isocyanate group equivalents are measured according to the following method.

Number of hydroxyl equivalents: JIS K1557,
Isocyanate group equivalent number: JIS K1556.

  Moreover, the urethane (meth) acrylate of the present invention can also be preferably produced by reacting the polyalkylene oxide (A) with the (meth) acryloyl group-containing isocyanate compound (E).

  Here, the (meth) acryloyl group-containing isocyanate compound (E) is not particularly limited as long as it is a compound having an isocyanate group and a (meth) acryloyl group. Examples thereof include acryloyloxyalkyl isocyanate compounds and methacryloyloxyalkyl isocyanate compounds. Specific examples of commercially available (meth) acryloyloxyalkyl isocyanate compounds include 2-methacryloyloxyethyl isocyanate (Showa Denko, Karenz MOI), 2-acryloyloxyethyl isocyanate (Showa Denko, Karenz). AOI), 1,1-bis (acryloyloxymethyl) ethyl isocyanate (manufactured by Showa Denko KK, Karenz BEI) and the like.

  When the polyalkylene oxide (A) and the (meth) acryloyl group-containing isocyanate compound (E) are reacted, the mixing ratio of the polyalkylene oxide (A) and the (meth) acryloyl group-containing isocyanate compound (E) is 0.00. 5 ≦ [number of hydroxyl group equivalents of (A) / isocyanate group equivalent number of (E)] ≦ 5.0 is preferably satisfied in the temperature range of 30 to 90 ° C., and 0.8 ≦ ([( It is more preferable to carry out in the temperature range of 60 to 80 ° C. with A) hydroxyl group equivalent number / (E) isocyanate group equivalent number] ≦ 3.0.

  It does not specifically limit as a reaction method at the time of making a polyalkylene oxide (A) and a (meth) acryloyl group containing isocyanate compound (E) react, and obtaining urethane (meth) acrylate. For example, polyalkylene oxide (A), (meth) acryloyl group-containing isocyanate compound (E) and, if necessary, other active hydrogen compounds, urethanization catalyst, solvent, antifoaming agent, other additives, etc. Examples thereof include a method of urethanization reaction in the presence. Therefore, the obtained urethane (meth) acrylate and the active energy ray-curable resin composition containing the urethane (meth) acrylate and a photopolymerization initiator may contain a urethanization catalyst, an antifoaming agent, an additive and the like.

  Here, examples of the urethanization catalyst include the urethanization catalyst described above.

  Although it does not specifically limit as reaction temperature at the time of making a polyalkylene oxide (A) and a (meth) acryloyl group containing isocyanate compound (E) react, It is preferable that it is the range of 50 to 130 degreeC.

  When a urethane (meth) acrylate is obtained by reacting an isocyanate group (NCO group) -containing urethane prepolymer (C) with a hydroxyl group-containing (meth) acrylate (D), or a polyalkylene oxide (A) and a (meth) acryloyl group In any case, when a urethane (meth) acrylate is obtained by reacting with the isocyanate compound (D), a polymerization inhibitor is added to the reaction system in order to control the radical polymerization reaction due to the heat of the (meth) acrylic group. Or may be reacted in the presence of oxygen.

  Examples of the polymerization inhibitor include orthonitrotoluene, hydroquinone, hydroquinone monomethyl, hydroquinone monomethyl ether, copper chloride and the like. These may be one kind or a mixture of two or more kinds. Moreover, the addition amount of a polymerization inhibitor has the preferable range of 50-5000 ppm with respect to a hydroxyl-containing (meth) acrylate (D) or a (meth) acryloyl group containing isocyanate compound (E).

  Next, the active energy ray-curable resin composition of the present invention will be described.

  The active energy ray-curable resin composition of the present invention contains the urethane (meth) acrylate of the present invention described above and a photopolymerization initiator. An active energy ray-curable resin composition in which a photopolymerization initiator is added as a catalyst is intended to advance the polymerization reaction (curing) by irradiating active energy rays to the urethane (meth) acrylate of the present invention. It is preferable.

  Examples of the photopolymerization initiator include benzoin such as benzoin, benzoin methyl ether, and benzoin isopropyl ether, or aromatic ketones such as benzophenone and benzoylbenzoic acid, α-dicarbonyls such as benzyl, and benzyldimethyl ketal. Benzyl ketals such as benzyl diethyl ketal, acetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 -Phenyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinopropanone-1 etc. Acetophenones, anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, thioxanthones such as 2,4-dimethylthioxanthone, 2-isopropylthioxanthone, 2,4-diisopropylthioxanthone, bis ( Phosphine oxides such as 2,4,6-trimethylbenzoyl) -phenylphosphine oxide, α-acyl oximes such as 1-phenyl-1,2-propanedione-2- [o-ethoxycarbonyl] oxime, p- Examples include amines such as ethyl dimethylaminobenzoate and isoamyl p-dimethylaminobenzoate. In addition, although a photoinitiator is excellent in surface curability and excellent in internal curability, it is preferable to use 2 or more types together.

  In addition, the urethane (meth) acrylate or active energy ray-curable resin composition of the present invention is within a range that does not impair the spirit of the invention, and, if necessary, an organic solvent for dilution, an ultraviolet absorber, an antioxidant, Various stabilizers such as light stabilizers, surface conditioners, thickeners, antistatic agents, plasticizers and the like may be added as appropriate.

  Here, the organic solvent for dilution is added as necessary to facilitate the application of the urethane (meth) acrylate or the active energy ray-curable resin composition of the present invention to the substrate.

  Examples of such organic solvents for dilution include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, propanol, and butanol, methyl ethyl ketone, 2- Examples thereof include ketones such as pentanone and isophorone, esters such as ethyl acetate, butyl acetate and methoxypropyl acetate, cellosolve solvents such as ethyl cellosolve, and glycol solvents such as methoxypropanol and methoxybutanol. These can be used alone or in combination.

  Examples of the ultraviolet absorber include benzotriazole-based or hydroxyphenyltriazine-based compounds. The content is 10 parts by weight or less, preferably 4 parts by weight or less, with respect to 100 parts by weight of the urethane (meth) acrylate or active energy ray-curable resin composition of the present invention.

  Examples of the antioxidant include compounds having an effect of suppressing oxidation of a polymer chain, such as a thioether compound, a phosphorus antioxidant, and a hindered phenol compound. Product names include Irganox manufactured by Ciba, Adeka Stub manufactured by Adeka, and the like.

  Among these, as an antioxidant, Preferably it is a hindered phenol type antioxidant, and since it is easy to obtain the antioxidant property with respect to urethane, 2, 6-di-t-butyl- 4-methylphenol (BHT) It is more preferable to use at least one antioxidant selected from IRGANOX-1010, IRGANOX-1024, IRGANOX-1035, IRGANOX-1076, and IRGANOX-1081 manufactured by Ciba Japan.

  The above-mentioned light stabilizer is not particularly limited, but the effect of imparting light resistance, weather resistance, and the like such as ultraviolet absorbers such as benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, hindered amine compounds, etc. There are some compounds, and as a trade name, chinuvin manufactured by Ciba Japan Co., Ltd. can be mentioned. The content thereof is 2 parts by weight or less, preferably 1 part by weight or less based on 100 parts by weight of the urethane (meth) acrylate or the active energy ray-curable resin composition of the present invention.

  Among these, as the light stabilizer, it is preferable to use at least one selected from Tinuvin 234, Tinuvin 144, Tinuvin C353, and Tinuvin B75.

  In the present invention, these antioxidants and light stabilizers can also be mixed and used.

  The above-mentioned surface conditioner imparts good wettability and uniformity of the coating film with respect to the base material, smoothness and slipperiness of the coating film surface, and silicone and acrylic copolymer type are representative. However, a silicone type is particularly preferable. Examples of the silicone-based surface conditioner include modified silicone obtained by modifying polydimethylsiloxane, polydimethylsiloxane, and the like. Examples of the modified silicone include polyether-modified products, alkyl-modified products, and polyester-modified products. Of these, polyether-modified products are most preferred.

  The above thickener is added to adjust the paint to an optimum viscosity for coating, and a cellulose-based or synthetic clay-based one is representative. Among these, the cellulose type is preferable in terms of the thickening effect, and specific examples include cellulose acetate and nitrocellulose. Among them, cellulose acetate is most preferable.

  The above-mentioned antistatic agent is added to impart an appropriate conductivity to the cured product when the active energy ray-curable resin composition of the present invention is cured with ultraviolet rays, for example, to obtain an effect such as prevention of dust adhesion. Examples thereof include surfactants, metal oxides, and conductive polymers. Of these, metal oxides and conductive polymers are preferable from the antistatic effect. Examples of metal oxides include zinc oxide and tin oxide. Examples of conductive polymers include polyethylene dioxythiophene and polyaniline.

  Examples of the plasticizer include phthalate esters, non-aromatic dibasic acid esters, aliphatic esters, polyalkylene glycol esters, phosphate esters, trimellitic acid esters, chlorinated paraffins. , Hydrocarbon oils, process oils, polyethers, epoxy plasticizers, polyester plasticizers, and the like. Of these, phthalates are preferred. Specifically, dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, dioctyl phthalate, dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, tricresyl phosphate, tributyl phosphate, epoxidized soybean oil , Epoxy benzyl stearate and the like. These plasticizers may be used alone or in admixture of two or more.

  In the active energy ray-curable resin composition of the present invention, a filler may be blended within a range not impairing the gist of the present invention, and is appropriately selected according to the purpose of blending.

  Such a filler is not particularly limited, and any filler such as an inorganic filler, an organic filler, or a fibrous filler can be selected and used.

  For example, fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid silica, fatty acid treated calcium carbonate, heavy calcium carbonate, calcium carbonate such as colloidal calcium carbonate, carbon black , Magnesium carbonate, magnesium hydroxide, iron oxide, zinc oxide, diatomaceous earth, calcined clay, clay, talc, titanium oxide, barium sulfate, kaolin, zeolite, bentonite, organic bentonite, aluminum, flint powder, pigment, shirasu balloon, glass Examples include microballoons, phenol resin / vinylidene chloride resin, polyvinyl chloride / polymethyl methacrylate, synthetic resin powders such as polystyrene, asbestos, glass fibers, glass filaments, and the like. These fillers can be used alone or in admixture of two or more kinds, and may be surface-treated with an appropriate surface treatment agent.

  Of these, inorganic fillers are preferred from the viewpoint of contamination, elastic modulus, and durability of the resulting polyurethane composition, fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silica. Silica such as acid, hydrous silicic acid, calcium carbonate treated with fatty acid, heavy calcium carbonate, colloidal calcium carbonate, carbon black, magnesium carbonate, magnesium hydroxide, iron oxide, zinc oxide, diatomaceous earth, calcined clay, clay Preferred examples include pigments such as talc, titanium oxide, barium sulfate, kaolin, zeolite, bentonite, organic bentonite, aluminum and flint powder.

  In addition to the photopolymerization initiator described above for the urethane (meth) acrylate of the present invention, if necessary, an organic solvent for dilution, various stabilizers and surface conditioners, thickeners, antistatic agents, plasticizers, fillers In order to obtain the active energy ray-curable resin composition of the present invention, various dispersion methods can be mentioned as preparation methods. As a stirrer, for example, a general-purpose stirrer, a disperser disperser, a dissolver, a kneader, a mixer, a lab plast mill, a planetary mixer, and the like can be used. It may be performed while operating.

  Moreover, it is preferable that the active energy ray-curable resin composition of the present invention is liquid or pasty in a normal temperature environment from the viewpoint of workability.

  Furthermore, urethane (meth) acrylate used for the active energy ray resin composition of the present invention, photopolymerization initiator, organic solvent for dilution, various stabilizers, surface conditioner, thickener, antistatic agent, plasticizer, filling The agent or the like is preferably dehydrated and used by vacuum heating or the like, but can also be used without dehydration in terms of workability and curability.

  The urethane (meth) acrylate or active energy ray-curable resin composition of the present invention is polymerized by irradiation with active energy rays, and a cured product having a crosslink is obtained depending on the molecular structure of the urethane (meth) acrylate. These cured products are suitably used, for example, as a coating film on a substrate.

  The cured coating film of the active energy ray-curable resin composition of the present invention is applied to the substrate by, for example, the conventionally known roll coating, flow coating, bar coating, etc. Then, it is obtained by irradiating with active energy rays and curing. Although the base material to apply | coat is not specifically limited, As a resin base material, the resin base material etc. which consist of a polycarbonate, an impact-resistant acrylic, a polystyrene, a polyester-type resin, an ABS resin, and these mixtures etc. are mentioned, for example.

  The active energy ray-curable resin composition of the present invention can be cured by irradiating active energy. Examples of active energy rays include electron beams, γ rays, and light rays, and ultraviolet rays are preferred as the light rays. .

  Here, as a light source for irradiating ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, or the like can be used.

  Cured products and cured coatings obtained by irradiating active energy rays to the active energy ray-curable resin composition of the present invention include various paints and adhesives, vehicles for printing ink, solder resist inks, letterpress materials, It is suitably used for applications such as mortar floor lining materials, PVC tile coatings, optical fiber coating materials, and plastic coating materials.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not construed as being limited to the following examples without departing from the gist thereof.

  In addition, in this invention, the property of an isocyanate group (NCO group) containing urethane prepolymer (C) changes by changing the kind of polyalkylene oxide (A) or polyisocyanate (B).

  Moreover, the property of urethane (meth) acrylate also changes with the property of (D) by making an isocyanate group (NCO group) containing urethane prepolymer (C) and a hydroxyl-containing (meth) acrylate (D) react.

  Furthermore, the properties of urethane (meth) acrylate obtained by reacting polyalkylene oxide (A) with (meth) acryloyl group-containing isocyanate compound (E) are polyalkylene oxide (A) and (meth) acryloyl group-containing. It varies depending on the type of isocyanate compound (E).

  Therefore, when the active energy ray-curable resin composition containing the urethane (meth) acrylate of the present invention and the photopolymerization initiator is irradiated with an active energy ray and cured, the physical properties of the cured product are also the above (C) and (D ), (A), and (E) vary depending on the nature and type. However, even if a cured product having different physical properties is obtained by changing (C), (D), (A), (E), stickiness of the cured product due to the degree of unsaturation in (A) and accompanying it Since contamination of the cured product is common, in the examples and comparative examples, stickiness was mainly evaluated. Furthermore, Mw / Mn obtained by GPC method using polystyrene as a standard substance affects the coatability of the composition when the active energy ray-curable composition of the present invention is used as a coating film. The evaluation of the coating property of the energy ray curable composition was also taken into consideration.

  The raw materials and evaluation methods used in the following examples and comparative examples are as shown below.

(material)
<Polyalkylene oxide (A)>
In the examples or comparative examples, polyoxypropylene glycol (PPG) was used as the polyalkylene oxide (A). The PPG used and its properties are shown in Tables 1 and 2. Table 1 is for a bifunctional PPG with two hydroxyl groups in one molecule, and Table 2 is for a trifunctional PPG with three hydroxyl groups in one molecule.

  Polyalkylene oxides A1 to A3: Dehydration and desolvation were sufficiently performed using a combination of an imino group-containing phosphazenium salt (IPZ) catalyst and triisopropoxyaluminum, and dehydration was sufficiently performed to a bifunctional PPG having a molecular weight of 400. Bifunctional PPG added with propylene oxide.

  Polyalkylene oxide A4: Commercially available PPG (PP-2000 manufactured by Sanyo Chemical Industries).

  Polyalkylene oxide A5: Commercially available PPG (PP-4000 manufactured by Sanyo Chemical Industries).

  Polyalkylene oxide A6: PPG obtained by adding propylene oxide to bifunctional PPG having a molecular weight of 400 using a double metal cyanide complex (DMC) catalyst.

  Polyalkylene oxides A7 and A8: Dehydration and desolvation are sufficiently performed using an imino group-containing phosphazenium salt (IPZ) catalyst and triisopropoxyaluminum in combination, and a trifunctional polyoxypropylene polyol (PPG) having a molecular weight of 400 Trifunctional PPG obtained by adding sufficiently dehydrated propylene oxide to

  Polyalkylene oxide A9: Commercially available PPG (FA-921 manufactured by Sanyo Chemical Industries).

  Polyalkylene oxide A10: trifunctional PPG obtained by adding propylene oxide to polyoxypropylene polyol (PPG) having a trifunctional molecular weight of 400 using only an imino group-containing phosphazenium salt (IPZ) catalyst by a conventional method.

  The polyalkylene oxide (A) was used after heating and vacuum dehydration before use. Moreover, the catalyst was removed and used by the conventional method except the commercial item.

  Here, as for polyalkylene oxide A1, A2, A3, A7, A8, Mw / Mn calculated | required by the degree of unsaturation and GPC method is in the range of this invention.

  On the other hand, polyalkylene oxides A4, A5, A9, and A10 have Mw / Mn within the scope of claims, but the degree of unsaturation is outside the scope of the present invention, and polyalkylene oxide (A6) has an unsaturation degree. Although it is within the scope of the present invention, Mw / Mn is out of the scope of the present invention.

<Polyisocyanate>
Examples of the polyisocyanate include HDI isocyanurate (coronate HX manufactured by Tosoh Corporation, hereinafter referred to as “polyisocyanate B1”) and 4,4′-diphenylmethane diisocyanate (4,4′-MDI, manufactured by Millionate MTL manufactured by Tosoh Corporation). B2 "). Table 3 shows the polyisocyanates B1 and B2 used in Examples or Comparative Examples and their properties.

<Isocyanate group-containing urethane prepolymer (C)>
Table 4 shows the isocyanate group (NCO group) -containing urethane prepolymer (C) used in Examples or Comparative Examples obtained by reacting the polyalkylene oxide (A) and the polyisocyanate (B), and their properties.

<Hydroxyl group-containing (meth) acrylate (D)>
As the hydroxyl group-containing (meth) acrylate (D), 2-hydroxyethyl acrylate (2HEA, hereinafter referred to as “hydroxyl group-containing (meth) acrylate D1”) and dipentaerythritol pentaacrylate (DPPA, hereinafter “hydroxyl group-containing (meth) acrylate) D2 ”). Table 5 shows the hydroxyl group-containing (meth) acrylates D1 and D2 and their properties used in Examples and Comparative Examples.

<(Meth) acryloyl group-containing isocyanate compound (E)>
As the (meth) acryloyl group-containing isocyanate compound (E), 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko KK, hereinafter referred to as “(meth) acryloyl group-containing isocyanate compound E1”) and 1,1-bis (Acryloyloxymethyl) ethyl isocyanate (Karenz BEI manufactured by Showa Denko KK, hereinafter referred to as “(meth) acryloyl group-containing isocyanate compound E2”) was used. Table 6 shows the (meth) acryloyl group-containing isocyanate compounds E1 and E2 and their properties used in Examples and Comparative Examples.

<Additives>
Photopolymerization initiator: Benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one Urethane catalyst: Dibutyltin dilaurate Polymerization inhibitor: Hydroquinone monomethyl (Evaluation method)
<Hydroxyl value, number average molecular weight>
The hydroxyl value (OHV) of the polyalkylene oxide was measured according to the method of JIS-K1557-1. The number average molecular weight of the polyalkylene oxide was calculated using the above formula (4) based on the hydroxyl value of the polyalkylene oxide.

<Unsaturation>
It measured according to the method of JIS-K1557-6.

<Ratio of weight average molecular weight Mw and number average molecular weight Mn (Mw / Mn)>
A sample was obtained by adding 10 mg of polyol and 10 ml of THF to a sample bottle, allowing it to stand for 1 night to dissolve, and filtering with a PTFE cartridge filter (0.5 μm). RI detector RI8020 as a detector, Tskel SuperH4000 × 2 and Tskel SuperH3000 × 2 manufactured by Tosoh Co., Ltd. in which a separation column is packed with a packing material having a particle size of 3 μm as a measurement column are connected in series. 5 tubes were connected, special grade tetrahydrofuran containing BHT stabilizer manufactured by Wako Pure Chemical Industries, Ltd. was used as the developing solvent, the flow rate on the separation column side was 0.6 ml / min, the flow rate on the reference side was 0.15 ml / min, the column temperature was 40 The analysis was performed at a temperature of ° C. The molecular weight distribution (Mw / Mn) was analyzed using a cubic approximate curve using 8 standard polystyrenes manufactured by Tosoh Corporation with known molecular weight as a calibration curve. Tosoh HLC-8320GPC was used for the measuring device, and Tosoh HLC-8320GPC-ECOSEC-WorkStation was used for the analysis.

<Workability of active energy ray-curable resin composition>
A mold release agent was applied to a mold having a thickness of about 2 mm and both sides of about 150 mm, filled with an appropriate amount of an active energy ray-curable resin composition, and stretched with a spatula so that the thickness became 2 mm. The ease of the stretching operation at that time was evaluated as follows as the workability.

Workability ○: Can be easily stretched with a spatula at room temperature Workability ×: Cannot be stretched easily with a spatula due to excessive viscosity at room temperature <Stickness of cured product (contamination)>
A silicone mold release agent was applied to a mold having a thickness of about 2 mm and sides of about 150 mm, filled with an appropriate amount of an active energy ray-curable resin composition, and stretched with a spatula so that the thickness was 2 mm. The active energy ray was irradiated after that, the resin composition in a metal mold | die was hardened, and the cured coating film was obtained. At room temperature, keep it in contact with the outside air to prevent dust and dust from sticking for 2 weeks, then spray silica sand No. 7 on the cured coating at room temperature and let it stand upside down for 1 minute. The state of the remaining deposits was observed. The evaluation criteria were as follows.

○: Adhesion of silica sand is not observed (less than 5% of surface area)
Δ: Slightly adhered silica sand can be removed by tapping (remaining less than 5% of the surface area)
X: Adherence of silica sand is observed and remains on the surface even when tapped (remaining 5% or more of the surface area)
Example 1.
Polyalkylene oxide A1 was put into a four-necked separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with a drying tube, and dehydrated under reduced pressure at 100 ° C. for 2 hours. After cooling to room temperature, under nitrogen, polyisocyanate B1 is placed in the same separable flask so that the molar ratio of NCO and OH (NCO / OH) is 1.5 with respect to A1, and at 60 ° C. under nitrogen. Add 100 ppm of octyltin dilaurate as a urethanization catalyst, stir until the consumption of NCO groups stops while following the absorption of NCO groups at 2270 cm -1 in the infrared absorption spectrum, and isocyanate group (NCO group) -containing urethane prepolymer C1 was obtained.

Next, the liquid temperature in the separable flask was lowered to 40 ° C., 500 ppm of octyltin dilaurate was added to the separable flask containing the obtained E1, and 400 ppm of hydroquinone monomethyl as a polymerization inhibitor was added. The liquid temperature was raised to 60 ° C., and the hydroxyl group-containing (meth) acrylate D1 was blended so that [number of hydroxyl group equivalents of D1 / isocyanate group equivalent number of C1] was 1.0, and 2270 cm in the infrared absorption spectrum. After stirring until the consumption of NCO groups of ^-1 was stopped, the mixture was stirred and then cooled to room temperature to obtain urethane (meth) acrylate F1.

  Furthermore, the obtained separable flask containing F1 has 3% by weight of benzophenone and 1% by weight of 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one as a photopolymerization initiator. Thus, the active energy ray-curable resin composition G1 was obtained by stirring under nitrogen at 60 ° C. and then cooling to room temperature.

  Here, the obtained G1 was filled in a mold having a surface of about 2 mm in thickness and about 150 mm on both sides coated with a silicone release agent, and stretched with a spatula so that the thickness was 2 mm. The ease of stretching was evaluated. As a result, G1 had a low viscosity, was easy to stretch after the mold was inserted, and the workability was good.

  Further, G1 in the mold was irradiated with ultraviolet rays as active energy rays at room temperature to cure G1. In addition, an 80 W / cm high-pressure mercury lamp was used for ultraviolet irradiation, the distance between the lamp and the cured product was set to 15 cm, and the ultraviolet irradiation time for the cured product was 5 seconds. When the stickiness of the obtained cured product was evaluated, it was a cured coating film with little stickiness and hardly contaminated. The results are shown in Table 7.

Example 2
An isocyanate group (NCO group) -containing urethane prepolymer C2 was prepared using A2 in place of the polyalkylene oxide A1, and the urethane (meth) acrylate F2 obtained therefrom and the active energy ray-curable resin composition G2 were used. The evaluation was the same as in Example 1. The results are also shown in Table 7. The obtained F2 had a low viscosity, G2 was easy to stretch after the mold was introduced, and the workability was good. Further, the UV cured product of G2 was a cured coating film with little stickiness and resisting contamination.

Example 3
An isocyanate group (NCO group) -containing urethane prepolymer C3 was prepared using A3 in place of the polyalkylene oxide A1, and a urethane (meth) acrylate F3 obtained therefrom and an active energy ray-curable resin composition G3 were used. The evaluation was the same as in Example 1. The results are also shown in Table 7. The obtained F3 had a low viscosity, G3 was easy to stretch after the mold was introduced, and the workability was good. Further, the UV-cured product of G3 was a cured coating film with little stickiness and resisting contamination.

Comparative Example 1
An isocyanate group (NCO group) -containing urethane prepolymer C4 was prepared using A4 in place of the polyalkylene oxide A1, and a urethane (meth) acrylate F4 obtained therefrom and an active energy ray-curable resin composition G4 were used. The evaluation was the same as in Example 1. The results are also shown in Table 7. The obtained F4 had a low viscosity, G4 was easy to stretch after the mold was introduced, and the workability was good. On the other hand, since the degree of unsaturation of A4 is out of the range of the present invention, the UV cured product of G4 was a cured coating film that was easily soiled with an evaluation of stickiness Δ.

Comparative Example 2
An isocyanate group (NCO group) -containing urethane prepolymer C5 was prepared using A5 instead of the polyalkylene oxide A1, and the urethane (meth) acrylate F5 obtained therefrom and the active energy ray-curable resin composition G5 were used. The evaluation was the same as in Example 1. The results are also shown in Table 7. The obtained F5 had a low viscosity, was easy to stretch after the mold was introduced, and the workability was good. On the other hand, since the degree of unsaturation of A5 deviates significantly from the scope of the present invention, the UV cured product of G5 was a cured coating film that was easily soiled with an evaluation of stickiness x.

Comparative Example 3
An isocyanate group (NCO group) -containing urethane prepolymer C6 was prepared using A6 instead of the polyalkylene oxide A1, and the urethane (meth) acrylate F6 obtained therefrom and the active energy ray-curable resin composition G6 were used. The evaluation was the same as in Example 1. The results are also shown in Table 7. The UV-cured product of G6 was a cured coating film with little stickiness and resisting contamination. On the other hand, since Aw is out of the scope of the present invention, Mw / Mn obtained by GPC using polystyrene as a standard substance is outside of the scope of the present invention. It was inferior in nature.

Example 4
A urethane prepolymer C2 containing an isocyanate group (NCO group) containing A2 in place of the polyalkylene oxide A1, and a urethane (meth) acrylate F7 obtained using D2 instead of the hydroxyl group-containing (meth) acrylate D1, And it evaluated similarly to Example 1 except having used active energy ray hardening resin composition G7. The results are also shown in Table 7. The obtained F7 had a low viscosity, G7 was easy to stretch after the mold was put in, and the workability was good. Moreover, the G7 ultraviolet-cured product was a cured coating film with little stickiness and resisting contamination.

  In addition, the cured coating film of Example 4 obtained using D2 was higher in hardness than the cured coating film of Example 2 obtained using D1.

Comparative Example 4
An urethane group (NCO group) -containing urethane prepolymer C5 is prepared using A5 instead of the polyalkylene oxide A1, and a urethane (meth) acrylate F8 obtained using D2 instead of the hydroxyl group-containing (meth) acrylate D1, And it evaluated similarly to Example 1 except having used active energy ray hardening resin composition G8. The results are also shown in Table 7. The obtained F8 had a low viscosity, and G8 was easy to stretch after the mold was introduced, and the workability was good. On the other hand, the UV cured product of G8 was a cured coating film that was easily soiled with an evaluation of stickiness of x.

  The cured coating film of Comparative Example 4 obtained using D2 was higher in hardness than the cured coating film of Comparative Example 2 obtained using D1, but the stickiness evaluation remained as x. It was.

Example 5 FIG.
An isocyanate group (NCO group) -containing urethane prepolymer C7 was prepared using A7 in place of polyalkylene oxide A1 and B2 in place of polyisocyanate B1, urethane (meth) acrylate F9 obtained therefrom, and active energy ray Evaluation was performed in the same manner as in Example 1 except that the curable resin composition G9 was used. The results are shown in Table 8. The obtained F9 had a low viscosity, G9 was easy to stretch after the mold was introduced, and the workability was good. Further, the UV cured product of G9 was a cured coating film with little stickiness and resisting contamination.

Example 6
An isocyanate group (NCO group) -containing urethane prepolymer C8 is prepared using A8 in place of polyalkylene oxide A1 and B2 in place of polyisocyanate B1, and urethane (meth) acrylate F10 obtained therefrom, and active energy ray Evaluation was performed in the same manner as in Example 1 except that the curable resin composition G10 was used. The results are also shown in Table 8. The obtained F10 had a low viscosity, G10 was easy to stretch after the mold was introduced, and the workability was good. Further, the UV cured product of G10 was a cured coating film with little stickiness and resisting contamination.

Example 7
An isocyanate group (NCO group) -containing urethane prepolymer C8 was prepared in the same manner as in Example 6, and the ratio of the number of isocyanate groups equivalent to C8 to the number of hydroxyl equivalents of D1, that is, [number of hydroxyl equivalents of D1 / isocyanate equivalent of C8] The number] was set to 4.0, and evaluation was performed in the same manner as in Example 6 except that urethane (meth) acrylate F11 obtained therefrom and active energy ray-curable resin composition G11 were used. The results are also shown in Table 8. Even when [D1 hydroxyl group equivalent number / C8 isocyanate group equivalent number] was 4.0, the obtained F11 had low viscosity, G11 was easy to stretch after the mold was put in, and the workability was good. . Further, the ultraviolet-cured product of G11 was a cured coating film with little stickiness and resisting contamination.

Comparative Example 5
An isocyanate group (NCO group) -containing urethane prepolymer C9 is prepared using A9 in place of polyalkylene oxide A1 and B2 in place of polyisocyanate B1, and urethane (meth) acrylate F12 obtained therefrom, and active energy ray Evaluation was performed in the same manner as in Example 1 except that the curable resin composition G12 was used. The results are also shown in Table 8. The obtained F12 had a low viscosity, G12 was easy to stretch after the mold was introduced, and the workability was good. On the other hand, since the degree of unsaturation of A9 deviates from the scope of the present invention, the UV cured product of G12 was a cured coating film that was easily soiled with an evaluation of a stickiness of Δ.

Comparative Example 6
An isocyanate group (NCO group) -containing urethane prepolymer C10 is prepared using A10 in place of polyalkylene oxide A1 and B2 in place of polyisocyanate B1, and urethane (meth) acrylate F13 obtained therefrom, and active energy ray Evaluation was performed in the same manner as in Example 1 except that the curable resin composition G13 was used. The results are also shown in Table 8. The obtained F13 had a low viscosity, G13 was easy to stretch after the mold was introduced, and the workability was good. On the other hand, since the degree of unsaturation of A10 greatly deviates from the scope of the present invention, the UV cured product of G13 was a cured coating film that was easily soiled by evaluation of stickiness x.

Example 8 FIG.
An isocyanate group (NCO group) -containing urethane prepolymer C8 is prepared using A8 instead of polyalkylene oxide A1 and B2 instead of polyisocyanate B1, and obtained using D2 instead of hydroxyl-containing (meth) acrylate D1. Evaluation was performed in the same manner as in Example 1 except that the obtained urethane (meth) acrylate F14 and the active energy ray-curable resin composition G14 were used. The results are also shown in Table 8. The obtained F14 had a low viscosity, G14 was easy to stretch after the mold was put in, and the workability was good. Further, the ultraviolet-cured product of G14 was a cured coating film with little stickiness and resisting contamination.

  In addition, the cured coating film of Example 8 obtained using D2 was higher in hardness than the cured coating film of Example 6 obtained using D1.

Comparative Example 7
An isocyanate group (NCO group) -containing urethane prepolymer C10 is prepared using A10 instead of polyalkylene oxide A1 and B2 instead of polyisocyanate B1, and obtained using D2 instead of hydroxyl-containing (meth) acrylate D1. Evaluation was performed in the same manner as in Example 1 except that the obtained urethane (meth) acrylate F15 and the active energy ray-curable resin composition G15 were used. The results are also shown in Table 8. The obtained F15 has a low viscosity, G15 was easy to stretch after the mold was put in, and the workability was good. On the other hand, the UV cured product of G15 was a sticky cured coating film with an evaluation of stickiness x. there were.

  In addition, although the cured coating film of Comparative Example 7 obtained by using D2 had higher hardness than the cured coating film of Comparative Example 6 obtained by using D1, the evaluation of stickiness was still x. It was.

Example 9
The polyalkylene oxide A2 was put into a four-necked separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with a drying tube, and dehydrated under reduced pressure at 100 ° C. for 2 hours. After cooling to room temperature, under nitrogen, (meth) acryloyl group-containing isocyanate compound E1 is placed in the separable flask so that the molar ratio of NCO to OH (NCO / OH) is 1.1 with respect to A2. Add 500 ppm of octyltin dilaurate as a urethanization catalyst, 400 ppm of hydroquinone monomethyl as a polymerization inhibitor, raise the temperature of the liquid in the separable flask to 60 ° C., and absorb 2270 cm −1 of NCO groups in the infrared absorption spectrum. Stirring until the consumption of NCO groups ceased to obtain urethane (meth) acrylate F16.

  In the same separable flask containing F16 obtained, 3% by weight of benzophenone and 1% by weight of 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one were used as a photopolymerization initiator. The resultant mixture was stirred at 60 ° C. under nitrogen, and then cooled to room temperature to obtain an active energy ray-curable resin composition G16.

  The obtained G16 is filled in a mold having a silicone release agent applied to the surface of about 2 mm in thickness and about 150 mm on both sides, and is stretched with a spatula so that the thickness is 2 mm. Was evaluated. As a result, the obtained F16 had a low viscosity, and G16 was easy to stretch after the mold was introduced, and the workability was good.

  Further, G16 in the mold was irradiated with ultraviolet rays as active energy rays at room temperature to cure G16. In addition, an 80 W / cm high-pressure mercury lamp was used for ultraviolet irradiation, the distance between the lamp and the cured product was set to 15 cm, and the ultraviolet irradiation time for the cured product was 5 seconds. When the stickiness of the obtained cured product was evaluated, it was a cured coating film with little stickiness and hardly contaminated. The above results are shown in Table 9.

Comparative Example 8.
Evaluation was performed in the same manner as in Example 9 except that urethane (meth) acrylate F17 was prepared using A5 instead of polyalkylene oxide A2, and the active energy ray-curable resin composition G17 obtained therefrom was used. The results are also shown in Table 9. The obtained F17 had a low viscosity, and G17 was easy to stretch after the mold was put in, and the workability was good. On the other hand, since the degree of unsaturation of A4 deviates greatly from the scope of the present invention, the UV-cured product of G17 was a cured coating film that was easily soiled by an evaluation of stickiness x.

Example 10
Urethane (meth) acrylate F18 was prepared using A8 instead of polyalkylene oxide A2 and E2 instead of (meth) acryloyl group-containing isocyanate compound E1, and the active energy ray-curable resin composition G18 obtained therefrom was prepared. Evaluation was performed in the same manner as in Example 9 except that it was used. The results are also shown in Table 9. The obtained F18 had a low viscosity, was easy to stretch after the G18 mold was put in, and the workability was good. Further, the ultraviolet-cured product of G18 was a cured coating film with little stickiness and resisting contamination.

  In addition, the cured coating film of Example 10 obtained using F18 (the number of functional groups of the hydroxyl group in A8 is 3 and the number of functional groups of the (meth) acryloyl group in E2 is 2) is F16 (in A2 The number of functional groups of the hydroxyl group was 2 and the number of functional groups of the (meth) acryloyl group in E1 was 1), and the hardness was higher than that of the cured coating film of Example 9.

Comparative Example 9
Urethane (meth) acrylate F19 was prepared using A10 in place of polyalkylene oxide A2 and E2 in place of (meth) acryloyl group-containing isocyanate compound E1, and active energy ray-curable resin composition G19 obtained therefrom was prepared. Evaluation was performed in the same manner as in Example 9 except that it was used. The results are also shown in Table 9. The obtained F19 had a low viscosity, and G19 was easy to stretch after the mold was put in, and the workability was good. On the other hand, the UV-cured product of G19 was a cured coating film that was easily soiled with an evaluation of stickiness of x.

  In addition, the cured coating film of Comparative Example 9 obtained using F19 (the number of functional groups of the hydroxyl group in A10 is 3 and the number of functional groups of the (meth) acryloyl group in E2 is 2) is F17 (in A5 The hardness of the cured coating film of Comparative Example 8 obtained using the number of functional groups of the hydroxyl group of 2 and the number of functional groups of the (meth) acryloyl group in E1 was 1) was higher. Remained x.

Claims (9)

It contains a urethane bond obtained by reacting a hydroxyl group present in the polyalkylene oxide (A) with an isocyanate group present in the polyisocyanate (B), and has a (meth) acryloyl group having one or more functional groups at the terminal. And the urethane (meth) acrylate characterized in that the polyalkylene oxide (A) satisfies all of the following (a1) to (a4).
(A1) The degree of unsaturation is 0.010 meq / g or less.
(A2) The number average molecular weight calculated from the hydroxyl value (OHV) is 1000 or more.
(A3) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) using polystyrene as a standard substance is 1.039 or less.
(A4) The number average molecular weight (M) calculated from Mw / Mn and hydroxyl value (OHV) determined by gel permeation chromatography (GPC) using polystyrene as a standard substance is expressed by the following formula (1). Fulfill.

Mw / Mn of polyalkylene oxide (A) obtained by the GPC method using polystyrene as a standard substance is connected in series to four columns packed with a 3 μm particle size filler in a separation column, and a resistance tube is connected to the reference side. 2. The urethane (meth) acrylate according to claim 1, wherein the urethane (meth) acrylate is a molecular weight distribution analyzed under conditions using tetrahydrofuran as a connecting and developing solvent. The polyalkylene oxide (A) is obtained by ring-opening polymerization of an alkylene oxide using a catalyst in which an imino group-containing phosphazenium salt and a Lewis acid are used in combination. The urethane (meth) acrylate according to claim 2. Isocyanate group (NCO group) -containing urethane prepolymer (C) obtained by reacting polyalkylene oxide (A) and polyisocyanate (B), and hydroxyl group-containing (meth) acrylate having one or more acryloyl groups ( The method for producing urethane (meth) acrylate according to any one of claims 1 to 3, wherein D) is reacted. Polyisocyanate (B) is polymethylene polyphenylene polyisocyanate (polymeric MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 1 , 5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, these 5. The product according to claim 4, which is at least one selected from the group consisting of isocyanate-containing prepolymers of the above and modified products of these isocyanates. Method. The polyalkylene oxide (A) is reacted with a (meth) acryloyl group-containing isocyanate compound (E) having a (meth) acryloyl group having one or more functional groups. The manufacturing method of urethane (meth) acrylate as described in 2.   An active energy ray-curable resin composition comprising the urethane (meth) acrylate according to any one of claims 1 to 3 and a photopolymerization initiator. A cured product of the active energy ray-curable resin composition according to claim 7. A cured coating film of the active energy ray-curable resin composition according to claim 7.