JP3301447B2 - Urethane / unsaturated organo oligomers and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urethane / unsaturated organo-oligomer which is used as a curable component in various inks, paint coatings or adhesives and which is cured by active energy rays, and a method for producing the same.

[0002]

2. Description of the Related Art Oligomers that can be cured by active energy rays such as ultraviolet rays, such as urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, and polyester (meth) acrylate oligomers, have been known. Especially urethane (meta)
Acrylate oligomers are tough, have high mechanical strength and form excellent polymers that are resistant to chemicals due to their chemical structure. In particular, the cured polymer has excellent adhesion to various substrates and good workability. For this reason, urethane (meth) acrylate oligomers are used in various fields as base agents in various inks, paint coating agents or adhesives of the type that can be cured by active energy rays.

[0003]

The oligomer used as a curing component in inks, paint coatings, adhesives, etc., is sometimes required to be a polymer having both high strength and high elongation. A polymer cured in the case of a conventional curable oligomer has a high strength and a low elongation. When the elongation is large, there is a problem that the strength is small. For example, a specific urethane oligomer synthesized by reacting a low molecular weight polyol with a diisocyanate compound is known as an oligomer that becomes a polymer having high tensile strength when cured. Such an oligomer is called a hard type and has no elongation at all.
Conversely, some oligomers have an increased elongation when polymerized. In this case, it is called a soft type, and the tensile strength is significantly reduced. Generally, oligomers are either hard or soft. A hardening agent that hardens in a well-balanced manner in both strength and elongation has not been obtained.

[0004] In the case of conventional oligomers of the type cured by active energy rays, particularly, urethane acrylate oligomers are characterized by being excellent in curability. However, even with such a property, there is a problem that the property cannot be fully utilized in this case, and its application range is also limited.

The present invention has been made to solve the above-mentioned problems, and a novel urethane / unsaturated organo oligomer which becomes a polymer having a large tensile strength and elongation when cured with an active energy ray such as ultraviolet rays, and its novel. It is intended to provide a manufacturing method.

[0006]

The urethane / unsaturated organo-oligomer of the present invention made to achieve the above object has a repeating unit of-[O (CH ₂ ) ₆ OOC].
- and ··· (a), - [O (CH _{2) 5} OOC]
− ・ ・ ・ (B) is included, and the ratio of (a) and (b) is
9: 1 to 1: 9, a number average molecular weight of 10 ³ to 10 obtained by linking a copolycarbonate having a hydroxy group at the terminal and having a number average molecular weight of 800 ± 200 and an organic isocyanate in a chain.
The urethane oligomer of No. ⁵ has an unsaturated organooxycarbonylimide group (-NHCOO-R = R) bonded to the terminal.

[0007] Such a urethane / unsaturated organo oligomer is represented by the following formula, for example.

R = ROOCNHR ² NHCO (OR ¹ OOCNHR ² NHCO) _n OR ¹ OOCNHR ² NHCOOR = R (I) R ¹ in the formula is represented by a form in which a hydroxyl group is eliminated from both terminals. It is a divalent residue of a copolycarbonate and is a copolymer group containing hexamethylene carbonate represented by the above formula (a) and pentamethylene carbonate represented by the above formula (b) in a main repeating unit. Adjacent repeating units may be the same or different. The repetition may be regular or irregular. R ¹ is represented, for example, by the following formula.

-[(CH ₂ ) ₆ OOC] _p [O (CH ₂ ) ₅ OOC] _q O (CH ₂ ) ₅ -In the formula, p and q are integers. The content ratio of hexamethylene carbonate (a) to pentamethylene carbonate (b) is desirably 9: 1 to 1: 9, preferably 7.5: 2.5 to 1.5: 8.5. When R ¹ is a copolymer of only hexamethylene carbonate (a) and pentamethylene carbonate (b) as in the above formula, the ratio of both is particularly 7.5: 2.5 to 1.
When in the range of 5: 8.5, the oligomers are effectively amorphous.

R ¹ is hexamethylene carbonate (a)
And pentamethylene carbonate (b), but may be composed of, but as a repeating unit in the copolymer, a residue in which the polyol is represented by leaving hydroxyl groups at both ends thereof, for example, 1,4- butanediol residues [- (CH _{2) 4} -], trimethylolpropane residues _{[-CH 2 C (CH 2 OH)} (C 2 H 5) CH 2 - ], trimethylol ethane residue [-CH ₂ C (CH ₂ OH) (CH ₃ ) CH _2- ], hexanetriol residue such as (-(CH ₂ ) ₄ CH (OH) CH _2- ], heptanetriol residue such as (-(CH ₂ ) ₅ CH (OH ) CH _2- ] and a pentaerythritol residue [-CH ₂ C (CH ₂ OH) ₂ CH _2- ]. The proportion of the contained polyol residue is 20 mol% or less in the case of 1,4-butanediol residue, based on the sum of hexamethylene carbonate (a) and pentamethylene carbonate (b).
Preferably, it is 15 mol% or less. In the case of residues of the above-mentioned polyols other than 1,4-butanediol, the content is desirably 10 mol% or less. When a polyol residue is included,
Even when the ratio between hexamethylene carbonate (a) and pentamethylene carbonate (b) is in the range of 9: 1 to 1: 9, which exceeds the range of 7.5: 2.5 to 1.5: 8.5, gelation of oligomers is effectively prevented. Is done.

As described above, the copolycarbonate is formed of hexamethylene carbonate (a), pentamethylene carbonate (b), and other polyols as a repeating unit. Number average molecular weight is 800 ± 2
00, preferably 800 ± 100. In particular, the number average molecular weight is 700 to 800, and the ratio between hexamethylene carbonate (a) and pentamethylene carbonate (b) is
When the ratio is 5: 5, the polymer generally has an elongation of 4 when cured.
It exhibits excellent physical properties such as 00% and a strength of 200 kg · f / cm ² .

R ² is a divalent aliphatic group or an aromatic group represented by a form obtained by removing an isocyanate group from an organic isocyanate. Specific examples will be shown while appropriately showing an example of a synthesis reaction process. The same applies hereinafter. For example, toluene-2,4-diyl group, toluene-2,6-diyl group, 1-methylene-1,3,3-trimethylcyclohexane-5-yl group reacted with isophorone diisocyanate, hexamethylene group,
Diphenylmethylene group, (o, m or p,) - xylene diyl group _{[- (CH 3) 2 C 6} H 4 - ], methylene bis (cyclohexenyl) group _{[-C 6 H 10 CH 2 C 6} H 10 - ] , trimethyl hexamethylene group _{[- (CH 3) 3 C 6} H 9 - ], cyclohexane-1,3-dimethylene group _{[-CH 2 C 6 H 10 CH 2} - ], cyclohexane-1,4-dimethylene group, a naphthalene A 1,5-diyl group and a triphenylene thiophosphate group [(-C ₆ H ₄ ) ₃ P = S] reacted with tris (isocyanatophenyl) thiophosphate.

The above R ¹ and R ² are bonded by urethane to form a urethane oligomer. In the main chain, as long as the effects of the present invention are not impaired, the residue of water, low molecular weight polyol, polyamine or the like is further contained in the form of an ether bond or an imino bond. It is preferred to be longer. Examples of such a chain extending group include, for example, those represented by a residue of a polyester polyol, a polyether polyol, a polycarbonate polyol, a polyolefin polyol or the like, in which hydrogen in a hydroxy group is eliminated.

N in the above formula I is the number of repeating units in the oligomer, and is generally 1 to 100, preferably 1 to 10.

-R = R is an unsaturated organo group containing at least one double bond. An oxycarbonylimide group (—OOC) is added to the end of the urethane oligomer composed of R ¹ , R ^{2 and the} like.
NH-). The basic skeletons of the two Rs having a double bond may be the same or different. Examples of such unsaturated organo groups include a dimethylene acrylate group reacted with hydroxyethyl acrylate [-C ₂ H ₄ OOCCH = CH ₂ ], a trimethylene acrylate group reacted with hydroxypropyl acrylate, and a tetramethyl group reacted with hydroxybutyl acrylate. Examples include a methylene acrylate group. Further, a group obtained by reacting a caprolactone adduct or an alkylene oxide adduct is exemplified. For example, pentamethylenecarbonyloxydimethylene-acrylate [-(CH ₂ ) ₅ COOC ₂ H ₄ OO reacted with hydroxyethyl acrylate / caprolactone adduct
CCH = CH ₂ ], pentamethylenecarbonyloxy trimethylene-acrylate reacted with hydroxypropyl acrylate / caprolactone adduct, pentamethylenecarbonyloxytetramethylene-acrylate group reacted with hydroxybutyl acrylate / caprolactone adduct, and the like. Ethylene acrylate / ethylene oxide adduct reacted dimethyleneoxydimethylene-acrylate group [-C ₂ H ₄ OC ₂ H ₄ OOCCH = CH ₂ ], hydroxyethyl acrylate / propylene oxide adduct reacted methyl dimethylene oxydiene Methylene-acrylate group [-C ₂ H ₃ (CH ₃ ) OC ₂ H ₄ OOCCH = CH ₂ ], ethyldimethyleneoxydimethylene-acrylate group reacted with hydroxyethyl acrylate / butylene oxide adduct [-C ₂ H ₃ (C
_{2 H 5) OC 2 H 4} OOCCH = CH 2 ], and the like. In addition, the following groups may be mentioned.

A hydroxytrimethylene acrylate group reacted with glycerin monoacrylate [-C ₃ H ₅ (OH) OOCCH
= CH _2], ethylene Les sulfonyl carbonyloxy glycerin diacrylate were reacted - trimethylene - acrylate group _{[-C 3 H 5 (OOCCH = CH} 2) 2 ], glycidyl methacrylate acrylic acid adduct had reacted 1-ethyl-les sulfonyl carbonyloxy 5-methyl-3-oxa-4-oxo-5-hexen-1-yl group _{[-CH (CH 2 OOCCH = CH 2} ) CH 2 OOCC (CH 3) = CH 2 ],
Trimethylolpropane monoacrylate reacted 2-
Ethyl-2-hydroxymethyl-4-oxa-5-oxo-6-
Hepten-1-yl group (-CH ₂ C (CH ₂ OH) (CH ₂ CH ₃ ) CH ₂ OOCCH = C
H ₂ ], 2,2 ′, 2 ″ -tri (ethylenylcarbonyloxymethyl) ethyl group [—CH ₂ C (CH ₂ OOCCH = CH ₂ ) ₃ ], pentaerythritol triacrylate reacted, dipentaerythritol 4-oxa-reacted with pentaacrylate
2,2 ′, 6,6 ′, 6 ″ -penta (ethylenylcarbonyloxymethyl) -hexyl group [—CH ₂ C (CH ₂
OOCCH = CH ₂ ) ₂ CH ₂ OCH ₂ C (CH ₂ OO
CCH = CH ₂ ) ₃ ] and 2,6,6′-tri (ethylenylcarbonyloxymethyl) -2-ethyl-4-oxa-octyl group [—CH ₂ C (CH ₂ CH ₃ ) (CH ₂ OOCCH = CH ₂ ) CH ₂ OCH ₂ C (CH ₂ OOCCH
= CH ₂ ) ₂ CH ₂ CH ₃ ], 2-ethyl-2-ethylenylcarbonyloxymethyl-4,7-dioxa-8-oxo-9-decene reacted with trimethylolpropane / ethylene oxide adduct / diacrylate -1-yl group (-CH ₂ C (C ₂ H ₅ ) (CH ₂ OOCCH = CH ₂ ) C
H ₂ OC ₂ H ₄ OOCCH = CH ₂ ], 5,5′-di (ethylenylcarbonyloxymethyl) -3-oxa-heptyl group [—CH ₂ CH ₂ OCH ₂ C
_{(CH 2 OOCCH = CH 2)} 2 C 2 H 5 ], trimethylolpropane propylene oxide adduct diacrylate it was reacted 4,7-dioxa-2-ethyl-2-ethyl-les sulfonyl carbonyloxy-5-methyl - 8-oxo-9-decen-1-yl group (-CH ₂ C (C _{2
H 5) (CH 2 OOCCH =} CH 2) CH 2 OC 2 H 3 (CH 3) OOCCH = CH 2 ], 2-methyl-5,5'-di (ethylene Les sulfonyl carbonyloxy-methyl) -
3-oxa-heptyl group (-C ₂ H ₃ (CH ₃ ) OCH ₂ C (CH ₂ OOCCH = C
H ₂ ) ₂ C ₂ H ₅ ]. Other examples include groups in which each ethylenyl group is partially changed to a 1-methylethylenyl group [— (CH ₃ ) C = CH ₂ ].

Such a urethane / unsaturated organo oligomer is synthesized as follows.

As a repeating unit,-[O (CH ₂ ) ₆ O
OC] - ... and (a), - [O (CH _{2) 5} O
A copolycarbonate having a number average molecular weight of 800 ± 200 having a ratio of (a) to (b) of from 9: 1 to 1: 9, and having a hydroxy group at a terminal, comprising: The polyisocyanate is subjected to a polyaddition reaction with an organic isocyanate to form a urethane oligomer having an isocyanate group (-N = C = O) at a terminal, and the terminal isocyanate group is subjected to an addition reaction with a hydroxy group of a hydroxy unsaturated compound.

The copolycarbonate to be subjected to the polyaddition reaction with the organic isocyanate contains the above hexamethylene carbonate (a), pentamethylene carbonate (b), and other polyol residues as necessary, and these are included in the repeating unit. Then, a copolycarbonate which is bonded in a chain at a predetermined ratio, further has hydroxy groups at both ends, and has the above molecular weight is used. The copolycarbonate is synthesized by charging a predetermined polyol into a reactor and reacting it with, for example, phosgene while controlling the molecular weight.

Examples of the organic isocyanate to be reacted with the copolycarbonate include the following known aromatic or aliphatic diisocyanates. 2,4-toluene diisocyanate (molecular weight 174) [CH ₃ C ₆ H
₃ (NCO) ₂ ], 2,6-toluene diisocyanate (molecular weight 17
4), isophorone diisocyanate (molecular weight 222) [(C
H ₃ ) ₃ C ₆ H ₇ (NCO) (CH ₂ NCO)], hexamethylene diisocyanate (molecular weight 168) [OCN (CH ₂ ) ₆ NCO], diphenylmethane diisocyanate (molecular weight 250) [(C ₆ H ₅ ) ₂ C (NCO) ₂ ),
(O, p, or m) -xylene diisocyanate (molecular weight 188)
[(CH ₃ ) ₂ (C ₆ H ₂ ) (NCO) ₂ ], methylene bis (cyclohexyl isocyanate) (molecular weight 262) [CH ₂ [(C ₆ H ₁₀ ) (NC
O)] ₂ ], trimethylhexamethylene diisocyanate (molecular weight 210) [(CH ₃ ) ₃ C ₆ H ₉ (NCO) ₂ ], 1,3- or 1,4-
(Isocyanatomethyl) cyclohexane (molecular weight 194)
[C ₆ H ₁₀ (CH ₂ NCO) ₂ ], 1,5-naphthalenediisocyanate (molecular weight 210) [C ₁₀ H ₆ (NCO) ₂ ], triphenylmethane triisocyanate, tris (isocyanate phenyl)
Thiophosphate (molecular weight 417) [[C ₆ H ₄ (N
CO)] ₃ P = S]. In addition, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDI) may be a dimerized polymer. Examples of the organic isocyanate include the above-mentioned specific isocyanurate-modified, carbodiimidated and biuret-modified organic isocyanates.

In order to react the copolycarbonate with the organic isocyanate, for example, 0.01 to 1.0 mol, preferably 0.1 to 1.0 mol, of the organic isocyanate is mixed in excess with respect to the copolycarbonate, and dibutyltin is used as a catalyst. Dilaurylate [[CH ₃ (CH ₂ ) ₃ ] ₂ Sn [OOC (CH ₂ ) ₁₀ C
H ₃ ] ₂ ] and then heating the reaction at 60-120 ° C. Incidentally, when the excess ratio is 0.1 mol, generally, the formula I
The number n of repeating units is 10.

In the reaction between the copolycarbonate and the organic isocyanate, if the above-mentioned water, low molecular weight polyol, polyamine and the like are present together, the length of the main chain is appropriately increased.

An example of the reaction formula is shown below.

[0024]

Embedded image

In the formula, HO-R ¹ -OH represents a copolycarbonate and other polyols. R ² -N = C = O represents an organic isocyanate. n is an integer.

Next, an oxycarbonylimide group is formed at the terminal of the urethane oligomer thus synthesized, and the hydroxy unsaturated compound is polymerized. Examples of the hydroxy unsaturated compound used in the reaction include a monofunctional acrylate and a polyfunctional acrylate. As the monofunctional acrylate, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyethyl acrylate-caprolactone adduct [HO (CH ₂ ) ₅ COOC ₂ H ₄ OOCCH = CH ₂ ], Hydroxyethyl methacrylate-caprolactone adduct, hydroxypropyl (meth) acrylate-caprolactone adduct,
Hydroxybutyl (meth) acrylate-caprolactone adduct, hydroxyethyl acrylate-ethylene oxide adduct [CH ₂ = CHCOOC ₂ H ₄ OC ₂ H ₄ OH], hydroxyethyl methacrylate-ethylene oxide adduct, hydroxyethyl (meth) acrylate- Examples include propylene oxide adducts and hydroxyethyl (meth) acrylate-butylene oxide adducts. Examples of the polyfunctional acrylate include glycerin mono (meth) acrylate, glycerin di (meth) acrylate, and glycidyl methacrylate acrylic acid adduct [CH ₂ = CHCOOCH ₂ CH (OH) CH ₂ OOCC (CH ₃ ) = C
H ₂ ], trimethylolpropane monoacrylate [CH ₂ =
CHCOOCH ₂ C (CH ₂ OH) ₂ CH ₂ CH ₃ ], trimethylolpropane monomethacrylate, di (meth) acrylate, pentaerythritol trimethacrylate [CH ₂ = CHCOOCH ₂ C
(CH ₂ OH) (CH ₂ OOCCH = CH ₂ ) ₂ ], pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate [CH ₂ = CHCOOCH ₂ C (CH ₂ OH) (CH ₂ OOCCH = CH ₂ ) CH ₂ OCH
₂ C (CH ₂ OOCCH = CH ₂ ) ₃ ), dipentaerythritol pentamethacrylate, ditrimethylolpropane triacrylate (CH ₂ = CHCOOCH ₂ C (CH ₂ OH) (CH ₂ CH ₃ ) CH ₂ OCH ₂ C (CH ₂ CH
_{3) (CH 2 OOCCH = CH} 2) 2 ], ditrimethylolpropane trimethacrylate, trimethylolpropane - ethylene oxide adduct - diacrylate _{[CH 2 = CHCOOCH 2 C (CH} 2 OC 2 H 4 O
H) (C ₂ H ₅ ) CH ₂ OOCCH = CH ₂ , CH ₂ = CHCOOC ₂ H ₄ OCH ₂ C (CH ₂ OH) (C
_{2 H 5) CH 2 OOCCH =} CH 2 ], trimethylolpropane - ethylene oxide adduct - dimethacrylate, trimethylolpropane - propylene oxide adduct - diacrylate [CH ₂ =
CHCOOCH ₂ C (C ₂ H ₅ ) (CH ₂ OCH ₂ CH (OH) CH ₃ ) CH ₂ OOCCH = CH ₂ , CH
₂ = CHCOOCH ₂ C (C ₂ H ₅ ) (CH ₂ OH) CH ₂ OCH ₂ CH (CH ₃ ) OOCCH = CH
₂ ], trimethylolpropane-propylene oxide adduct-dimethacrylate and the like.

In order to carry out the addition reaction of the hydroxyl group of the hydroxy unsaturated compound to the terminal isocyanate group, for example, p-methoxyphenol and di-t-butyl-
In the presence of hydroxy-toluene or the like, 2 to 2.4 moles of the hydroxyunsaturated compound may be reacted with a catalyst such as dibutyltin dilaurate at 60 to 90 ° C. with respect to 1 mole of the urethane obtained above. The end point of the reaction is
For example, disappearance of the isocyanate group may be confirmed by an infrared absorption spectrum.

The reaction formula is shown below.

[0029]

Embedded image

The urethane / unsaturated organo oligomer obtained in this manner can be used in addition to the above-mentioned various monofunctional acrylates and polyfunctional acrylates, as well as phenoxyethyl acrylate (PO-A) [CH ₂ = CHCOOC ₂ H ₄ OC ₆ H _5] or trimethylolpropane - ethylene oxide adduct - as such diluent triacrylate, used by dissolving therein. The diluent is a polyfunctional acrylate of 0 to 50% by weight, usually 1 to 50% by weight, and a monofunctional acrylate of 5 to 50% by weight.
It is prepared by mixing at a ratio of 70% by weight. The concentration of the urethane / unsaturated organo oligomer to be mixed in the diluent is
50 ± 20% by weight. Further in the diluent, for example,
Hydroxycyclohexyl phenyl ketone (HOC ₆ H ₁₀ COC
₆ H ₅ ] is added at a ratio of 0.5 to 10% by weight. When the composition obtained by mixing the respective components is irradiated with ultraviolet rays, the urethane / unsaturated organo oligomer easily cures together with the diluent. The curing speed is fast, and the resulting polymer exhibits unprecedented high performance in toughness, flexibility and adhesion.

Such a urethane / unsaturated organo oligomer is used as a curing agent component such as various inks, paint coating agents or adhesives.

[0032]

As described in detail above, the urethane / unsaturated organo oligomer of the present invention, when cured,
Excellent properties such as toughness, flexibility and adhesion. According to the method for producing a urethane / unsaturated organo oligomer of the present invention, such excellent urethane / unsaturated organo oligomer can be synthesized.

[0033]

Embodiments of the present invention will be described below. In preliminary experiments 1 to 8, the copolycarbonate (PC-1 to P
C-8), and then using those copolycarbonates in Examples 1 to 10 and Comparative Examples 1 to 4,
Unsaturated organo oligomers were prepared and their physical properties were examined.

Preliminary experiment 1 1,6-hexanediol (a) and 1,5-pentaneddiol (b)
Were charged into a reactor at a molar ratio of a: b = 7.0: 3.0, and phosgene was introduced to form a copolycarbonate (PC
-1) was synthesized.

The OH value of the obtained PC-1 was 140.3 mg.
KOH / g, a viscous liquid with a molecular weight of 800.

Preliminary Experiments 2 to 9 The polyols shown in Table 1 were charged as reactants in the proportions shown in Table 1, and copolycarbonates (PC-2 to PC-9) were synthesized in the same manner as in Preliminary Experiment 1. In Experiment 4, 1,4-butanediol was used as the polyhydric alcohol,
In Experiment 5, trimethylolpropane was used as a polyhydric alcohol.

Table 1 shows the OH value, properties, average molecular weight, etc. together with the results of Preliminary Experiment 1.

[0038]

[Table 1]

Example 1 In a 5 liter reactor equipped with a stirrer, a thermometer and a condenser, 888 g of isophorone diisocyanate and the copolycarbonate (PC-1) produced in Preliminary Experiment 1 were added.
2400 g and 0.8 g of dibutyltin dilaurate were added, and the mixture was kept at 75 to 80 ° C. under a nitrogen atmosphere, and isophorone diisocyanate and copolycarbonate (PC-1) were added.
Was reacted for 3 hours to synthesize a urethane oligomer.

Next, the supply of nitrogen was stopped, and p-
0.7 g each of methoxyphenol and di-t-butyl-hydroxy-toluene were introduced, and 238 g of hydroxyethyl acrylate was further added. 75 ° C to 80 ° C
Then, the urethane oligomer in the reactor was reacted with hydroxyethyl acrylate for 4 hours to obtain a urethane / unsaturated organo oligomer. The end point of the reaction is determined by the infrared absorption spectrum of the isocyanate group absorption spectrum (228
0 cm ^-1 ) was confirmed.

As a curing agent, 1-phenyl-2-hydroxy-2-methylpropan-1-one (H
3.0 g of MPP (Darocure # 1173)
In addition, after sufficient mixing, the obtained mixture was applied on a glass plate to obtain a film having a thickness of 30 μm. The film is 6m
/ Min speed, and cured by irradiating light from a position of 10 cm height using a high-pressure mercury lamp (80 W / cm).

The hardness, tensile strength, elongation and average molecular weight of the obtained cured product were examined. Hardness is JIS K
It measured using the A-type hardness meter based on 6301. The tensile test and elongation were performed at a tensile speed of 300 mm / min in accordance with JIS K7113. The average molecular weight is determined by gel carrier liquid chromatography (GPC manufactured by Showa Denko
Using 1), the value was calculated as a value converted into polystyrene. Table 2 shows the results.

[0043]

[Table 2]

In the above table, IPDI indicates isophorone diisocyanate, HMDI indicates hexamethylene diisocyanate, and HEA indicates hydroxyethyl acrylate. I
4 moles of PDI correspond to 888 g. 2 moles is 444
g. 2.05 moles of HEA corresponds to 238 g. A in the hardness column is a value measured by an A-type hardness meter, and D is a value measured by a D-type hardness meter.

Examples 2 to 10 Each of the copolycarbonates (PCs) obtained in preliminary experiments 2 to 7
-2-PC-7) and hydroxyethyl acrylate in the proportions shown in Table 2, a urethane / unsaturated organo oligomer was synthesized and cured in the same manner as in Example 1, and its hardness, tensile strength and elongation were examined. Was. However, in Example 5, 1,2-dihydroxypropyl acrylate (G-1) was used as a chain extender of the urethane / unsaturated organo oligomer.
A) was used. The results are shown in Tables 2 to 4.

[0046]

[Table 3]

[0047]

[Table 4]

Comparative Examples 1 to 5 Copolycarbonates (PC-6, 8, 9), polypropylene glycol, hydroxyethyl acrylate, etc. obtained in preliminary experiments 6, 8, and 9 were used in the proportions shown in Tables 4 and 5, respectively. Other than that, it carried out similarly to Example 1.

[0049]

[Table 5]

Example 11 Using 50 parts of the urethane / unsaturated organo oligomer obtained in Example 4 as a base agent, 20 parts of phenoxyethyl acrylate (PO-A) and trimethylolpropane-ethylene oxide adduct-triol as diluents Acrylate (TM
P-3EOA) and 30 parts of hydroxycyclohexylphenyl ketone (HC) as a photopolymerization initiator.
HP) (3 parts), these were mixed, and the mixture was applied on a 1 mm thick vinyl chloride sheet at a thickness of 30 μm to obtain an oligomer coating.

Next, 1k is set at two points on a predetermined conveyor.
A w-high pressure mercury lamp was provided, the coating material was loaded on the conveyor and moved at a speed of 6 m / min, and the mixture was irradiated with ultraviolet rays to obtain a cured coating material.

The obtained cured coating material was subjected to a scratch resistance test, an adhesion check test, and a workability check test.
Table 6 shows the results of the scratch resistance test, and Table 6 shows the results of the adhesion confirmation test and the results of the workability confirmation test.

[0053]

[Table 6]

In the abrasion resistance test, a surface of # 100 steel wool was applied with a load of 1 kg, and the surface was rubbed for 10 reciprocations, and the condition of the surface was visually checked. A sample having no scratches in a range of 1 cm × 3 cm was evaluated as “〇”, a sample having 1 to 10 scratches in the above range was evaluated as “△”, and a case where countless scratches were formed was evaluated as “×”.

The adhesion test (cross-cut test) was performed as follows. Eleven straight grooves were cut vertically and horizontally on the coating film with a safety razor (multi-cross cutter) at a depth reaching the substrate while intersecting at a right angle to form 100 grids. Cellophane tape is strongly pressed on the grid,
Then, the tape was peeled off, and the number of grids in which the grooves did not disappear was counted. The initial number of grids of 100 was used as the denominator, the number of grids where the grooves did not disappear was used as the numerator, and the degree of adhesion was expressed as a fraction. The score was set to 0/100 when all the grids disappeared, and was set to 100/100 when all the grids remained.

In the workability test, a test piece having a length of 10 cm and a width of 5 cm was cut out from the obtained cured coating material, and the test piece was wrapped around the outer periphery of a cylindrical body having a diameter of 20 mm to check the state of the film. No abnormality was evaluated as Δ, slight cracks were evaluated as Δ, and a large number of cracks were evaluated as x.

Example 12 The procedure of Example 11 was repeated, except that the urethane / unsaturated organo oligomer obtained in Example 5 was used instead of the urethane / unsaturated organo oligomer obtained in Example 4. Table 6 shows the results.

Comparative Examples 6 and 7 The same procedures as in Example 3 were carried out except that the urethane / unsaturated organo oligomers obtained in Comparative Example 3 and Comparative Example 5 were used instead of the urethane / unsaturated organo oligomer obtained in Example 4. Same as 11. Table 6 shows the results.

From the above results, it was found that the urethane / unsaturated organo oligomer synthesized in Examples 4 and 5 was overall superior to Comparative Examples 6 and 7.

[0060]

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-145636 (JP, A) JP-A-4-7327 (JP, A) JP-A-3-247618 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08G 18/00-18/87 C08F 299/06 C09D 175/14-175/16

Claims (2)

(57) [Claims] 1. A repeating unit comprising-[O (CH ₂ ) ₆ OOC] -... (a) and-[O (CH ₂ ) ₅ OOC] -... (b), The ratio of a) to (b) is 9: 1 to 1: 9, the number average molecular weight of a copolycarbonate having a hydroxy group at the terminal and having a number average molecular weight of 800 ± 200, and an organic isocyanate linked in a chain. A urethane / unsaturated organo oligomer comprising 10 ³ to 10 ⁵ urethane oligomers each having an unsaturated organooxycarbonylimide group bonded to a terminal. 2. The composition of the present invention contains-[O (CH ₂ ) ₆ OOC]-... (A) and-[O (CH ₂ ) ₅ OOC]-. The ratio of a) and (b) is 9: 1 to 1: 9, a polycarbonate having a hydroxy group at the terminal and having a number average molecular weight of 800 ± 200, and a polyaddition reaction with an organic isocyanate,
A method for producing a urethane / unsaturated organo oligomer, comprising forming a urethane oligomer having an isocyanate group at a terminal, and subjecting the terminal isocyanate group to an addition reaction with a hydroxy group of a hydroxy unsaturated compound.