JPH0555528B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a modified polyurethane resin composition. [Prior Art] Polyurethane resins have been known as resins characterized by flexibility, and polymers of ethylenically unsaturated monomers have been known as resins characterized by toughness. [Problems to be Solved by the Invention] However, even if both resins are blended to obtain a resin composition that has the characteristics of each resin, there is a practical problem due to poor compatibility and poor stability. It was hot. [Means for Solving the Problems] The present inventors have arrived at the present invention as a result of intensive studies aimed at obtaining a resin composition that has all the characteristics of each resin and has good stability. . That is, the present invention comprises polyol (a), polyisocyanate (b), and the general formula [Wherein, R is H or CH ₃ , X is an alkylene group having 2 to 4 carbon atoms which may have a substituent, m is 1 to 5
, n is an integer of 0 to 5, and p represents 4 or 5], and optionally a chain extender.
Polyurethane resin (A) from (d) and/or polymerization terminator (e), organic solvent (S) and radical polymerization initiator
This modified polyurethane resin composition is obtained by polymerizing monomer (B) having one ethylenic double bond in the presence of (Z) and is in the form of a resin solution. Examples of the polyol (a) in the present invention include polyether diols and polyester diols. Examples of polyether diols include alkylene oxide adducts of low-molecular glycols; those obtained by ring-opening polymerization or ring-opening copolymerization (block and/or random) of alkylene oxides or cyclic ethers; and two or more of these. For example, combination use of Specific examples of the above-mentioned low molecular weight glycols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,
4-,1,3-butanediol, neopentyl glycol, 3-methylpentanediol, 1,6
-hexanediol, 1,8-octamethylene diol, alkyl dialkanolamine; low molecular weight diols having a cyclic group [e.g.
Items listed in No. 1474: bis(hydroxymethyl)cyclohexane, m- and p-xylylene glycol, bis(hydroxyethylbenzene, 1,4-
Bis(2-hydroxyethoxy)benzene, 4,
4'-bis(2-droxyethoxy)-diphenylpropane (ethylene oxide adduct of bisphenol A)], and combinations of two or more of these. Specific examples of the alkylene oxides include alkylene oxides having 2 to 4 carbon atoms (ethylene oxide, propylene oxide, 1,2-, 2,3
-, 1,3-butylene oxide, etc.), and examples of the cyclic ether include tetrahydrofuran. Specific examples of products obtained by ring-opening polymerization or ring-opening copolymerization of alkylene oxides or cyclic ethers include polyethylene glycol, polypropylene glycol, and polyoxyethylene/oxypropylene (block and/or random).
Glycol, polytetramethylene ether glycol, polytetramethylene ether oxyethylene (block and/or random) glycol, polytetramethylene ether oxypropylene (block and/or random) glycol, polyhexamethylene ether glycol, polyoctamethylene ether Examples include glycol. Examples of polyester diols include condensed polyester diols obtained by reacting low-molecular diols and/or polyether diols with a molecular weight of 1000 or less with dicarboxylic acids; polylactone diols obtained by ring-opening polymerization of lactones. Specific examples of the above-mentioned low molecular weight diols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4
- or 1,3-butanediol, neopentyl glycol, 3-methylpentanediol,
1,6-hexanediol, 1,8-octamethylenediol, alkyl dialkanolamine;
Low-molecular-weight diols having a cyclic group [for example, those described in Japanese Patent Publication No. 1474/1974: bis(hydroxymethyl)cyclohexane, m- and p-xylylene glycol, bis(hydroxyethylbenzene,
1,4-bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)-
diphenylpropane (ethylene oxide adduct of bisphenol A)], and combinations of two or more of these. Specific examples of the polyether diol having a molecular weight of 1000 or less include the polyether diols (polyethylene glycol, polytetramethylene ether glycol, polypropylene glycol, triethylene glycol, etc.), combinations of two or more of these, and the like. Specific examples of the dicarboxylic acids mentioned above include aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, etc.), Examples include combinations of two or more of these. Specific examples of the lactone include ε-caprolactone, γ-valerolactone, and the like. Polyester diols can be prepared using conventional methods, such as dicarboxylic acids or their ester-forming derivatives [anhydrides (maleic anhydride, phthalic anhydride, etc.), lower esters (dimethyl terephthalate, etc.)]. etc.), halides, etc.; or by adding a lactone to an initiator (low molecular diol and/or polyether diol with a molecular weight of 1000 or less). Specific examples of these polyester diols include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, poly-3-methylpentane adipate, polyethylene propylene adipate, polyethylene butylene adipate, polybutylene hexamethylene adipate, and polyester diol. Examples include diethylene adipate, poly(polytetramethylene ether) adipate, polyethylene azelate, polyethylene sebacate, polybutylene azelate, polybutylene sebacate, polycaprolactone diol, polyvalerolactone diol; and combinations of two or more of these. The average molecular weight (by hydroxyl value measurement) of polyol (a) is usually 200 to 5000, preferably 300 to 4000.
It is. In the present invention, the polyisocyanate (b) has, for example, a carbon number (excluding carbon in the NCO group) of 2
~12 aliphatic polyisocyanates, 4 to 15 carbon atoms
Examples include alicyclic polyisocyanates, aromatic aliphatic polyisocyanates having 8 to 12 carbon atoms, aromatic polyisocyanates having 6 to 20 carbon atoms, and modified products thereof. Specific examples of such polyisocyanate (b) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexane. Diisocyanate, lysine diisocyanate, 2,6-diisocyanate methyl caproate, bis(2-isocyanate ethyl) fumarate, bis(2-isocyanate ethyl) carbonate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate; isophorone diisocyanate ( IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanate ethyl) 4-cyclohexene-1,2-dicarboxylate; xylylene diisocyanate, tetra Methyl xylylene diisocyanate, diethylbenzene diisocyanate; water modified product of HDI, IPDI
Tolylene diisocyanate (TDI), crude TDI, diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (crude MDI), modified MDI (carbodiimide modified MDI, etc.), naphthylene diisocyanate; (carbodiimide group, uretdione group, uretimine group, urea group, biuret group and/or isocyanurate group-containing modified products, etc.); and combinations of two or more of these. Among these, the preferred ones in terms of weather resistance are:
These are aliphatic diisocyanates and cycloaliphatic diisocyanates. In the present invention, among X in general formula (1),
Examples of the alkylene group having 2 to 4 carbon atoms (without a substituent) include an ethylene group, a propylene group, and a butylene group. Examples of the substituent for X include a phenyl group and a halogen (Cl, Br, etc.) atom. 2-4 carbon atoms with substituents
Specific examples of alkylene groups include styrene group, α
-methylstyrene group, epichloro group, etc. m is usually an integer of 1 to 5, preferably 1 or 2. n is usually an integer of 0 to 5, preferably 0 or 1. p is 4 or 5, preferably 5. Specific examples of the compound (c) represented by general formula (1) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and ε-caprolactone-2-hydroxyethyl (meth)acrylate adduct. , γ-valerolactone-2-hydroxyethyl (meth)acrylate adduct, and the like. Chain extender (d) used as necessary in the present invention
are low-molecular polyfunctional active hydrogen compounds, such as the low-molecular glycols and their alkylene oxide low molar adducts (molecular weight less than 200), aliphatic diamines (ethylene diamine, hexamethylene diamine, etc.) mentioned as raw materials for the polyester diol. , alicyclic diamine (isophorone diamine, 4,
4'-dicyclohexylmethane diamine, etc.), aromatic diamines (4,4-diaminodiphenylmethane, etc.), araliphatic diamines (xylene diamine, etc.), alkanol diamines (ethanol ethylene diamine, etc.), hydrazine, dihydrazines (adipate dihydrazide, etc.) ), and combinations of two or more of these. Among these, preferred are low molecular weight glycols, alicyclic diamines, and combinations of two or more thereof. In addition, specific examples of the polymerization terminator (e) to be used if necessary include monovalent low molecular alcohols (methanol, butanol, cyclohexanol, etc.),
alkylamines (mono-, di-methylamines,
Examples include mono-, di-butylamine, etc.), alkanolamines (mono-, di-ethanolamine, etc.), and the like. In the present invention, the amount of chain extender (d) when producing polyurethane resin (A) is as follows with respect to polyol (a):
It is usually 50% by weight or less, preferably 30% by weight or less. The ratio of (a) and (d) to polyisocyanate (b) is such that the NCO/active hydrogen equivalent ratio is usually 1.05 to 2.0, preferably 1.1 to 1.8. The amount of compound (c) represented by general formula (1) is usually 0.3 to 30%, preferably 0.5 to 20%, based on the total weight of (a), (b) and (d).
%. The amount of polymerization terminator (e) is such that the weight ratio of (e) and (c) is usually 0/100 to 90/10, preferably 0/100 to
The amount is in the 80/20 range. (a), (c), (d) and
The ratio of active hydrogen-containing compound consisting of (e) and (b) is:
NCO/active hydrogen equivalent is usually 0.8 to 1.2, preferably
The range is 0.9 to 1.1. An example of the method for producing the polyurethane resin (A) is as follows:
A method of reacting (a) and (b) with (d) if necessary, and then reacting (c) and if necessary (e) until substantially no NCO group is contained; and all of these reaction components. There is a method of reacting all at once, and any method may be used. The polyurethane resin (A) is produced in the presence or absence of a solvent. Examples of such solvents include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, etc.), aromatic hydrocarbons (toluene, xylene, etc.), alcohols ( methanol, ethanol, isopropyl alcohol, etc.), polyhydric alcohol derivatives (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), amides (dimethylformamide, etc.), sulfoxides (dimethyl sulfoxide, etc.), and mixtures of two or more of these Examples include solvents. Among these, preferred are acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and two of these. It is a mixed solvent of more than one species. The amount of solvent used is such that the weight ratio of polyurethane resin (A) to solvent is 100/0 to 10/90, preferably 80/20 to
The amount is in the range of 20/80. The reaction temperature during the production of the polyurethane resin (A) is usually 20°C to 150°C, preferably 50°C to 120°C. In order to accelerate the reaction, amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.) and tin-based catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.) used in normal urethane reactions may be used. . Additionally, during the reaction of compound (c) represented by general formula (1), a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, P-methoxyphenol, or P-benzoquinone is added to prevent gelation due to radical polymerization. , for the reaction solids content
It is preferable to add 20 to 200 ppm. In the present invention, the organic solvent (S) includes the same ones as those exemplified above as the solvent in the production of (A), and preferred ones are also the same as above. Therefore, when (A) is produced in the presence of (S), there is an advantage that (A) can be used in a solution state in the next step of polymerizing (B). The amount of organic solvent (S) to be used is such that the solid content concentration of the modified polyurethane resin composition of the present invention is usually 10% by weight or more, preferably 20% by weight or more.
The amount is ~80% by weight. In the present invention, monomers (B) having one ethylenic double bond include the following (a) to (f). (a) (meth)acrylic acid and its derivatives: (meth)
Acrylonitrile; (meth)acrylic acid and their salts; methyl (meth)acrylate;
Alkyl (meth)acrylate (the number of carbon atoms in the alkyl group is usually 1 to 20, preferably 1 to 10) such as n-butyl (meth)acrylate; 2
-Hydroxyethyl (meth)acrylate, 2
- hydroxypropyl (meth)acrylate,
Hydroxyalkyl (meth)acrylic acid (alkyl group usually has 2 to 4 carbon atoms) esters and their lactone adducts such as ε-caprolactone-2-hydroxyethyl (meth)acrylate; aminoalkyl (meth)acrylate such as dimethylaminoethyl methacrylate; ) Acrylate; (meth)acrylic acid amide, etc. (b) Aromatic vinyl hydrocarbon monomer: styrene, α
- Methylstyrene, etc. (c) Vinyl halide monomers: vinyl chloride, vinylidene chloride, etc. (d) Olefin hydrocarbon monomers: ethylene, propylene, butadiene, isobutylene, isoprene, 1,4-pentadiene, etc. (v) Vinyl Ester monomers: vinyl acetate, etc. (f) Vinyl ether monomers: vinyl methyl ether, etc. Two or more of the above examples (a) to (f) may be used in combination. Among these, preferred are (a), (b) and (c). In the present invention, as the radical polymerization initiator (Z), azo compounds (such as azobisisobutylnitrile), peroxides (such as benzoyl peroxide), persulfates, perborates, etc. can be used.
Practically speaking, azo compounds and peroxides are preferred. The amount of the initiator (Z) used is not particularly limited, and is usually 0.05 to 10% by weight, preferably 0.05 to 10% by weight based on the monomer (B).
It is 0.1 to 5% by weight. When polymerizing the monomer (B) in the presence of the resin (A), the solvent (S) and the initiator (Z), the ratio of (A) and (B) used can vary over a wide range. It can be changed depending on the situation, but usually (A)
The weight ratio (A)/(B) of (solid content) and (B) is 95/5 ~
5/95, preferably 90/10 to 10/90. Along with this wide range of changes during production, the polymerization of the polyurethane moiety in the resin composition of the present invention and the ethylenically unsaturated monomer (monomer having one ethylenic double bond) There is also the advantage that the content ratio between the two parts can be varied over a wide range depending on the purpose. The temperature of polymerization reaction is usually 50℃~170℃
℃, preferably 70℃ to 150℃. The molecular weight (weight average molecular weight) of the modified polyurethane resin, which is the resin component in the resin composition of the present invention, is usually
2000-200000, preferably 5000-150000. The resin composition of the present invention is produced in the presence of an organic solvent (S) and is in the form of a resin solution. That is, it is a stable solution containing a modified polyurethane resin having both a polyurethane portion and a polymerized portion of an ethylenically unsaturated monomer. The viscosity of the resin composition of the present invention is usually 50-500000 cps/20°C, preferably 100-500000 cps/20°C.
100000cps/20℃. The resin composition of the present invention may contain auxiliary compounding agents if necessary. For example, coloring agents such as dyes and pigments for decorative coloring, inorganic fillers such as calcium carbonate and glass fiber, organic modifiers such as AS resin,
Various stabilizers to improve light resistance and heat deterioration resistance, softeners and plasticizers, and isocyanate-based crosslinking agents to improve strength, such as 1 mole of trimethylolpropane and 1,6-hexamethylene diisocyanate,
Examples include adducts synthesized from 3 moles of tolylene diisocyanate or isophorone diisocyanate. [Examples] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto. Parts in the examples are parts by weight. Synthesis Example 1 Synthesis of the polyurethane resin (A) 2000 parts of polybutylene adipate diol with a molecular weight of 2000 and 1,4-butanediol were placed in a three-necked flask equipped with a stirrer, a reflux condenser, and a nitrogen blowing tube.
After charging 135 parts and 666 parts of isophorone diisocyanate and heating to 100 to 120°C and reacting for 6 hours,
Cool to 80℃ and add 1245 parts of toluene, 68 parts of 2-hydroxyethyl methacrylate, 37 parts of butanol, 0.1 part of hydroquinone, dibutyltin dilaurate.
0.3 part was charged and the reaction was carried out at a temperature of 80 to 90℃.
The reaction was completed when the concentration of free isocyanate groups was about 0.05% or less. 1661 parts of toluene was added to make a homogeneous solution. Solids content 50%, viscosity
A polyurethane solution of 16000 cps/20°C was obtained. This product is designated as A-1. Synthesis Example 2 Synthesis of the polyurethane resin (A) Polytetramethylene glycol with a molecular weight of 1000
1000 parts, 4,4'-dicyclohexylmethane diisocyanate 316 parts, toluene 606 parts, e-caprolactone-2-hydroxyethyl methacrylate
100 parts of hydroquinone, 0.1 part of hydroquinone, and 0.15 parts of dibutyltin dilaurate were charged, and the reaction was carried out at a temperature of 80 to 90°C until the free isocyanate group concentration was approximately 0.05%.
The reaction was considered complete when the following values were reached. 808 parts of toluene was added to make a homogeneous solution. Solid content 50%,
A polyurethane solution with a viscosity of 20,000 cps/20°C was obtained.
This product is designated as A-2. Reference example 1 Synthesis of polyurethane without double bonds Polybutylene adipate diol with a molecular weight of 2000
1000 parts, 67 parts of 1,4-butanediol, and 333 parts of isophorone diisocyanate were added.
℃ and reacted for 6 hours, then cooled to 100℃, charged with 616 parts of toluene, 37 parts of butanol, and 0.15 parts of dibutyltin dilaurate, and reacted at a temperature of 90 to 100℃ until the free isocyanate group concentration was approx.
The reaction was considered complete when the concentration was 0.05% or less.
821 parts of toluene was added to make a homogeneous solution. Solid content
A polyurethane solution of 50% and a viscosity of 12000 cps/20°C was obtained. This product is designated as A-3. Example 1 Production of the resin composition of the present invention 600 parts of (A-1) obtained in Synthesis Example 1 and 165 parts of toluene were placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen blowing pipe, and a dropping funnel. Prepare and raise the temperature to 90-100°C while blowing nitrogen at a rate of 10 ml/min. A mixture of 190 parts of methyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 1.4 parts of azobisisobutyronitrile, and 50 parts of toluene was placed in a flask kept at a temperature of 90 to 100°C.
The mixture was added dropwise over a period of time to carry out a polymerization reaction. One hour after the completion of the dropwise addition, a mixed solution of 1.4 parts of azobisisobutyronitrile and 100 parts of toluene was further added dropwise over a period of 3 hours, and the reaction was completed by aging. Solid content 45
%, viscosity 15000cps/20℃, molecular weight of resin component approx.
A homogeneous and transparent solution of the resin composition of the present invention having a weight average molecular weight of 35,000 and a polyurethane content of about 60% in the solid content (modified polyurethane resin) was obtained. Reference Example 2 Synthesis of acrylic polymer A polymerization reaction was carried out in Example 1 without using (A-1), and the solid content was 45% and the viscosity was 11000 cps/20°C.
A transparent acrylic polymer solution with a molecular weight of about 30,000 was obtained. Example 2 Production of the resin composition of the present invention 200 parts of (A-1) obtained in Synthesis Example 1 and 216 parts of toluene were placed in a four-neck flask equipped with a stirrer, a reflux condenser, a nitrogen blowing pipe, and a dropping funnel. The temperature was raised to 90 to 100° C. while blowing nitrogen at a rate of 10 ml/min. A mixture of 380 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 4.0 parts of azobisisobutyronitrile, and 100 parts of toluene was placed in a flask kept at a temperature of 90 to 100°C.
The mixture was added dropwise over a period of time to carry out a polymerization reaction. One hour after the completion of the dropwise addition, a mixed solution of 2.8 parts of azobisisobutyronitrile and 200 parts of toluene was further added dropwise over a period of 3 hours, and the reaction was completed by aging. Solid content 45
%, viscosity 12000cps/20℃, molecular weight of resin component approx.
32000, a homogeneous transparent solution of a resin composition having a polyurethane content of about 20% in the solid content (modified polyurethane resin) was obtained. Example 3 Production of resin composition of the present invention A polymerization reaction was carried out in the same manner as in Example 2 except that 200 parts of (A-2) obtained in Synthesis Example 2 was used.
Solid content 45%, viscosity 40000cps/20℃, molecular weight approx.
50000, the content of polyurethane in the solid content is approximately 20
% of a modified polyurethane resin composition was obtained. Comparative Example 1 Production of mixed resin solution A polymerization reaction was carried out in the same manner as in Example 1, except that 600 parts of (A-3) obtained in Reference Example 1 was used.
Solid content 45%, viscosity 3000cps/20℃, molecular weight approx.
25000, the content of polyurethane in the solid content is approximately 60
A clear solution of % polyurethane mixed resin was obtained. Comparative Example 2 Production of mixed resin solution Polyurethane solution obtained in Reference Example 1 (A-3) was added to the acrylic polymer solution obtained in Reference Example 2.
was added in an amount such that the solid content ratio of (A-3) was 60% and mixed. The appearance of the obtained solution was opaque. Usage example 1 Use as a compatibilizer Modified polyurethane resin solution obtained in Example 1, urethane polymer solution (A-3) obtained in Reference example 1, and acrylic polymer solution obtained in Reference example 2 and the solid content ratio of each is 1/1/1
The following amounts were added and mixed. The resulting solution was homogeneous and transparent. Test Example Appearance of each solution obtained in Examples 1 to 3 and Comparative Examples 1 and 2 when finished, appearance after storage at room temperature for 1 month,
Further, the appearance of the film that was coated on a glass plate to a dry thickness of 0.2 mm and air-dried at room temperature for 3 days was observed, and the results shown in Table 1 below were obtained (○ indicates uniform transparency).

[Table] [Effects of the Invention] The resin composition of the present invention has a polyurethane moiety and an ethylenically unsaturated monomer (one ethylenically unsaturated monomer).
Since this solution contains a modified polyurethane resin having a polymerized portion of a monomer (individual monomer), this composition has both the flexibility of the polyurethane resin and the toughness of the ethylenically unsaturated monomer polymer. A cured product such as a film having a resin solution can be obtained, and the resin solution improves the blend type problem and has good stability. The ratio of the polyurethane portion to the polymerized portion of the ethylenically unsaturated monomer in the resin composition of the present invention can be arbitrarily changed and can be designed depending on the purpose of use. Furthermore, since the resin composition of the present invention has a polyurethane part and a polymerized part of an ethylenically unsaturated monomer, a compatibilizer when blending a polyurethane resin and an ethylenically unsaturated monomer polymer, That is, it is effective as an auxiliary agent that makes both resins compatible and contributes to stabilization after blending. Because of the effects described above, the resin composition of the present invention is suitable for applications such as paints, inks, and coating vehicles.

Claims (1)

[Claims] 1. Polyol (a), polyisocyanate (b),
general formula [Wherein, R is H or CH ₃ , X is an alkylene group having 2 to 4 carbon atoms which may have a substituent, m is 1 to 5
, n is an integer of 0 to 5, p represents 4 or 5], and optionally a chain extender.
Polyurethane resin (A) from (d) and/or polymerization terminator (e), organic solvent (S) and radical polymerization initiator
A modified polyurethane resin composition obtained by polymerizing a monomer (B) having one ethylenic double bond in the presence of (Z), and which is in the form of a resin solution.