JPS6090211A - Ionizing radiation curing urethane composition - Google Patents

Abstract

PURPOSE:The titled composition, consisting essentially of a reaction product of an isocyanate compound with a polyether, an alcohol or amine and an acrylate compound, and capable of solventless coating and giving hydrophilic films having improved physical properties. CONSTITUTION:A composition, consisting essentially of a product prepared by reacting four components of (A) a organic di- and/or triisocyanate with (B) di- and/or trihydroxypolyether, (C) a di- or trihydric organic alcohol and/or bifunctional amine compound and (D) an acrylate compound having groups selected from free hydroxyl groups and carboxyl groups in the molecule, e.g. 2-hydroxyethyl acrylate, and having two or more units consisting of the components (A) and (B) and one or more units of the component (C) in the molecule, and obtained by adding if necessary an ionizing radiation curing monomer thereto.

Description

Detailed Description of the Invention (Technical Field) The present invention can be applied without a bath agent, is non-polluting and safe, and has excellent moisture permeability, moisture absorption, and flexibility after curing.
The present invention relates to an ionizing radiation-curable urethane composition that provides a hydrophilic cured film with excellent physical properties such as elongation and tensile strength.

(Prior art) Conventionally, in order to obtain a cured film of hydrophilic polyurethane 41111m, a hydrophilic hydroxy group-containing polyether was used as the main component, and after obtaining a linear urethane polymer by addition polymerization with polyisocyanate, In order to improve the physical properties of urethane polymers, polyinsyanate is usually added during coating, and the solvent is evaporated and removed in the drying process after coating, followed by curing.

In the above-mentioned conventional V-tan polymer, a cured film with better physical properties can be obtained as the linear chain length increases, but as the content of polar groups such as urethane bonds increases, DMF has high dissolving power as solubility decreases.

A large amount of polar solvents such as MEK and THF must be used to dilute the coating, which not only requires a long drying oven to dry after coating, but also poses major health and safety and disaster prevention problems (solvent (problems attributable to).

In addition, in the method of crosslinking and curing by adding polyisocyanate, there is a limit to the amount of polyisocyanate added in order to prevent gelation before coating, and in addition, the reaction of polyisocyanate itself is slow, so there is a limit to the amount of polyisocyanate added. After coating, the heat applied in the drying oven does not sufficiently crosslink, and after coating and drying, it is necessary to carry out aging at a temperature of about 1I-θ to 70° C. for a certain period of time (the issue of crosslinking rate).

On the other hand, the use of ionizing radiation to cure polyether-based urethane compositions has been considered as a way to essentially improve the problems caused by solvents and crosslinking speeds, but there is still no hydrophilic It has not been possible to obtain a product that satisfies both sex and physical properties at the same time.

Examples of technologies related to hydrophilic urethane compositions that have been investigated to date are as follows.

■A compound in which acrylic groups are added to both ends of polytetramethylene glycol via urethane bonds (Tokukosho!7
3-//, No. 2933). In this compound, it is necessary that the chain length of the polytetramethylene compound is long,
As the chain length increases, the crosslinking density decreases and the cohesive force between the polyether main chains decreases, resulting in a decrease in physical properties such as tensile strength and elongation.

■An acrylic group is added to one end of alkoxypolyethylene glycol via a urethane bond (JP-A-Sho!
;'I-/AO'19q). In this compound, the longer the chain length of polyethylene glycol, the better the hydrophilicity, but conversely, the longer the chain length, the lower the content of acrylic groups, which slows down the curing speed even when irradiated with ionizing radiation. .

In both of (1) and (2) above, the lack of cohesive force between molecules due to the small number of urethane bonds in the main chain, and the small amount of acrylic groups contained lead to a decrease in the degree of curing.

The inventor of the present invention aims to overcome these drawbacks of the above-mentioned conventional techniques by introducing urethane bonds into the main chain to improve the cohesive force, and further by branching to improve the curability. The inventors have discovered a urethane composition that provides a cured film with excellent physical properties and hydrophilic properties by introducing an acrylic group into the side chain.

(Structure of the invention) Non-invention.

“(a) organic di- and/or tri-incyanate, (bl
di- and/or trihydroxy polyether, (c) =
A divalent or trivalent organic alcohol compound and/or a covalent organic amine compound, and (dl) containing at least 1 group selected from free hydroxyl and carboxyl groups in the molecule.
It is a reaction product obtained by reacting a component of a unique acrylate compound, and (a
) and (bl) have at least a repeating unit in one molecule, and an ionizing radiation-curable urethane whose main component is a reaction product having at least one unit in one molecule of (C) Its main purpose is the composition.

Typical structures of the ionizing radiation-curable urethane composition of the present invention include the following three embodiments.

(a) Soft segment consisting of diisocyanate and dihydroxy ether and alcohol amine) 1-
A structure in which an acrylic group is introduced at both ends of a linear main chain as a whole that has a do segment. A chain of branched compounds consisting of (ether) and (a) a structure in which three or more terminals are introduced with ac IJ) groups, and (c) the nodes in (a) above. A structure in which a linear chain containing a segment, an acrylate with a trifunctional active group, and an acrylate with a side chain consisting of a force and a force are introduced.

The above (a) to (1) are typical examples of the present invention, and may be other than these.

The reason why the urethane composition of the present invention satisfies both hydrophilicity and physical properties is firstly that hydrophilicity is expressed due to the presence of the d5 1J ether component, and also that the soft segment is present in the main chain. This is presumed to be because toughness is obtained by having a hard segment, and furthermore, by polyfunctionalization through branching and introduction of an acrylic group into the side chain, curing speed and mechanical strength are improved.

The organic di- or tri-insocyanate which is the starting component in the present invention refers to aliphatic and aromatic polyinsyanates having solid or tri-incyanate groups, more specifically tetramethylene diisocyanate, Hexamethinone diisocyanate, 2,4'-trilene diisocyanate, core 6-dolylene diisocyanate, diphenylmethane diisocyanate,
/, 5-naphthalene diisocyanate, 3,3-dimethylchloride, ri'-diphenylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, /, 3-bis(incyanatomethyl)cyclohexane, trimethylhexamete Diisocyanate, -),) liphenylmethane triincyanate, or the like can be mentioned. Two or more types of these polyinsyanates may be used in combination.

Next, the di- or trihydroxy polyether used as a starting component in the present invention includes, for example, polyethers obtained by monopolymerizing or copolymerizing ethylene oxide, propylene oxide, tetrahydrofuran, etc. Or hydroxy M
Polymers obtained by reacting Y-containing compounds such as trimethylolpropane, glycerin, hexanetriol, pentaerythritol, propylene glycol, and mercapto group-containing compounds, such as ethylene thioglycol, with the above-mentioned cyclic ethers such as ethylene oxide. Can you also name the ethers?

The third component, a covalent or trivalent organic alcohol compound or a divalent organic amine, forms a rigid hard segment with a high concentration of polar groups. The third component of the stiffness is selected so that the bonds formed by reacting with isocyanate have a rich hydrogen bonding ability and have a rigid structure with good symmetry in order to form an aggregated phase of hard segments. has been done. Specific examples include ethylenecrite, /, 4(-phthanediol, trimethylolpropane, triisopropanolamine, N,N-bis(2-
hydroxy)aniline, hydroquinone-bis(β-hydroxyethyl)v)ether, resorcinol-bis(β-hydroxyethyl)
- polyol compounds such as hydroxyethyl) ether,
3. Cudiaminodiphenyl meta-y; j-dichloro-+, lI'-diaminodiphenylmethane, /, 2-
Examples include polyamine compounds such as his(2-aminoneenylthio)ethane and trimethylene glycol valaminobenzoate.

Furthermore, the acrylate compound, which is the fourth starting component used in the present invention, has at least seven hydroxyl groups or carboxyl groups in the molecule, and more specifically, hydroxyethyl acrylate, hydroxypropyl Acrylate, hydroxybutyl acrylate, hydroxydiethyl methacrylate, hydroxyethyl acrylate, hydroxybutyl methacrylate, t-hydroxycyclohexyl acrylate), 5-hydroxycyclooctyl acrylate, S-hydroxycyclooctyl acrylate, euhydroxy-3-phenyloxopropyl Acrylate, acrylic acid, methacrylic acid, etc.
Alternatively, a compound containing seven active hydrogen groups can be used, such as an adduct of co-hydroxyethyl acrylate and phthalic anhydride.

Further, as starting materials, acrylate adducts include ethylene glycol diglycidyl ether dimethacrylate, diethylene glycol diglycidyl ether dimethacrylate, globylene dalycol didalicidyl ether diacrylate, phthalic acid diglycidyl ester diacrylate-1-, etc. , an addition reaction product of a jepoxy compound and acrylic acid, or a reaction with a glycidyl (meth)acrylate dibasic. Here,
Dibasic acids include itaconic acid, maleic acid, fumaric acid, cono-phosphoric acid, adipic acid, and terephthalic acid.

The urethane composition of the present invention is produced, for example, as follows.

■Excess di- or tri-incyanate is reacted with di- or trihydroxy-containing polyether, and a small amount (
A prepolymer having isocyanate groups at both ends is prepared, and then reacted with an alcohol equivalent or an amide equivalent of less than or equal to the incyanate equivalent of the divalent or trivalent alcohol or covalent amine t prepolymer to form a hard A prepolymer having a segment and both ends being incyanate is further reacted with an acrylate compound having a hydroxy group or a carboxyl group at both ends to produce a linear urethane compound having acrylates at both ends. .

■Hard segment obtained during the manufacturing method of ■ above)
A prepolymer having Y and having incyanate at both ends is reacted with an acrylate containing a hydroxy group or a carboxyl group, and has an acrylic group at one end,
A prepolymer having an isocyanate group at the other end is prepared and further reacted with trihydroxypolyether to produce a branched urethane compound.

(2) A di- or trihydroxy polyether is reacted with a di- or triisocyanate to prepare a prepolymer having an isocyanate group at the end.

Next, the dihydroxy group-containing acrylate and alcohol (or amine) are reacted to produce a urethane compound having an acrylic group in the 11411 chain.

Although the manufacturing methods (1) to (4) have been mentioned above, manufacturing methods other than these may be used.

In order to obtain the inventive V-tan composition, the reaction between the hydroxyl group, amine group or carboxyl group and the incyanate group can be carried out by a known method, and both reaction components are mixed and the temperature is set at θ~/θ0°C. The reaction may be caused by heating. In addition, it is possible to carry out the reaction without adding a solvent at the time of mixing, or in a bath agent that is not reactive with isocyanate groups. It is also possible to use monomers active towards sexual radiation. Further, triethylamine, piperazine, triethanolamine, dibutyltin dilaurate, stannath octoate, stannath laurate, dioctylna/dilaurate, etc. can be used for the purpose of promoting the reaction.

In addition, polymerization inhibitors that protect acrylic groups during the reaction between hydroxyl or carboxyl groups and incyanate groups, such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, Le et al.'i / 0-/ 000 ppm
It is good to add some degree.

The urethane compound obtained by the above starting materials and production method can be used alone as an ionizing radiation-curable urethane composition, but it may also be further diluted using a reactive diluent (reactive diluent The amount of addition is 7 to 100 parts by weight based on the heavy parts of the urethane compound or the ioθ parts by weight of the mixture of the urethane compound and the additive component (2).

Specifically, reactive diluents include monomers having ethylenically unsaturated bonds in the molecule, such as styrene monomers such as styrene and α-methylstyrene; methyl acrylate, λ-ethylhexyl acrylate, and acrylic acid. Acrylic acid esters such as methoxy/ethyl, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, acrylated phenyl; methyl methacrylate, ethyl methacrylate, globyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, Methacrylic acid esters such as phenyl methacrylate and methacrylic acid lauryl; unsaturated carboxylic acid amides such as acrylamide and methacrylamide; Substituted amino alcohols of unsaturated acids such as (amino)ethyl, co(N,N-shihendylamino)ethyl acrylate, (N,N-dimethylamino)methyl methacrylate, λ-(N,N-diethylaminobupropyl acrylate) 7
゜Ester MI N-methyl rubbermoyloxyethyl acrylate, N-ethyl rubbermoyloxy: f-f, n
'7 acrylate, N-butylcarbamoyloxyethyl acrylate, N-phenylcarbamoyloxyethyl acrylate), 2-(N-methylcarbamoyloxy]ethyl acrylate, λ-carbamoyloxyglobil acrylate, etc. Moloxyalkyl acrylates;
ethylene glycol diacrylate, propylene glycol diacrylate, neobentyldalicol diacrylate), A-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol dimethac 7 from polyfunctional compounds such as V-t, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc.
It can be used as a species or as a mixture of two or more species.

The inventive ionizing radiation curable urethane composition is used as follows.

First, when the composition is used as a coating layer, a coating film is applied to a substrate by a conventional coating method such as roll coating, gravure coating, fountain coating, curtain flow coating, wire barcoding, etc. Heating during coating 1-rot and coating, l
: Even easier.

Next, the painted film is irradiated with ionizing radiation.

As the ionizing radiation, electron beams, alpha rays, beta rays, gamma rays, ultraviolet rays, etc. can be used, and a sensitizer may be appropriately added to the composition.

Of the two advantages of ionizing radiation, the processing speed is slow.
In addition, it is preferable to use an electron beam because of its high transparency, and it is preferable to use an electron beam.
Each type of electron beam, such as a cylinder frequency type, is also emitted from a meter, and the temperature is θ~
/ 000 KeV, preferably /θ0~3θθKe
It is preferable to use an electron beam with an energy in the range of V.

(Effects of the Invention) According to the present invention, it is possible to obtain an industrial composition which has hydrophilicity and can provide a film with excellent physical properties after curing.

Therefore, the uninvented ionizing radiation curable urethane composition is
It can be used for textile processing, leather, building materials, furniture, etc., and exhibits properties such as moisture permeability, anti-fogging, and prevention of sweating.

(Examples) Examples will be given below to more specifically explain the present invention.

Example/ In a two-hole flask for Sl equipped with a stirrer, a thermometer, a condenser and a dropping funnel, xinin diisocyanate/, 3009 and dibutyltin dilaurate o, sg
While heating the contents of the flask to a temperature of 3 °C, add polyethylene glycol (molecules it-
2oθ)/, 2009 drops, then also 33
q,4'-diaminodiphenyl meta 72 while kept at ℃
19g of 9fK was added, and further 2/9g of euhydroxyethyl acrylate was added dropwise. After the addition, 9'l of hydroquinone was added, and after the addition, stirring was carried out at a temperature of 50°C for 3 hours.

The obtained compound was coated on a release paper so that the film thickness became SOμm, and after coating, an electron beam irradiation device manufactured by CESI, Electrocurtain CB, :voo/s o /, 7 o
) and press/7 to accelerate! ;KV, irradiation dose/θM
The coating film was cured by electron beam irradiation under rad conditions, and then peeled off to obtain a film.

When the performance of this film was evaluated, it was as follows.

Moisture permeability! 1300g/n? /x 4'hr growth
-〇 0% Tensile strength Sco θ 1 year old Example Same as Example /, except that xylylene diisocyanate 1, 7.2 gjj, dibutyltin dilaurate/, Og
, & N-phytylcarbamoyloxyethyl acrylate 3θθI, polyethylene glycol (molecular weight 2
00) g 00.9'ti1'la was lowered. After dropping, 90g of 4-butanediol was added dropwise while maintaining the temperature at 35''C, followed by addition of co-hydroxyethyl acrylate at a temperature of 50℃. A prepolymer having an acrylic group at one end and an isocyanate group at the other end was obtained.

996 g of polypropylene glycol triol (molecular weight 3000) was added dropwise to the prepolymer obtained above at SO° C. After the dropwise addition, hydroquinone/, 5 i @ was added, followed by stirring at a temperature of 30”c for 3 hours.

The following evaluation results were obtained in the same manner as in Examples.

Moisture permeability Jz k (70i/m/2'I
hr elongation 270% tensile strength, 21IO ~ Example 3 In the same manner as in Example, first, 900 g of xylylene diisocyanate, dibutyl diisocyanate V-)/, θ, 9.
&bi N-butylcarbamoylquine acrylate 3oog
In contrast, polyethylene glycol (molecular weight II 00
) /, 60θg was added dropwise to form a prepolymer having isocyanate groups at both ends, and further hydroquinone-bis(β-hydroxyethyl) ether gog and ethylene glycol diglycidyl ether diacrylate it
After that, add co-hydroxyethyl acrylate ggg at Sθ゛C, and then add hydroquinone/... After the addition, the mixture was stirred at a temperature of 50° C. for 3 hours.

Hereinafter, one song was evaluated in the same manner as in Example 1, and the results were as follows.

Moisture permeability J, 000 i/11(/2 hr
Elongation/g 0% Tensile strength 31I-θ″1.

Claims (1)

[Scope of Claims] fll(a) organic di- and/or triisocyanate, (
b) di- and/or trihydroxypolynee f, +1/,
(C) Divalent or trivalent organic alcohol adduct and/or
or a reaction obtained by reacting a λ-valent organic amine compound and (d) a free hydroxyl group, a carboxyl group, and the q component of an acrinaut compound having at least one free hydroxyl group or carboxyl group in the molecule. product, ta
) and (b) in the molecule, and the reaction product has 2 or more repeating units in the molecule, and the ionizing radiation-curable component has the unit of (C) in the molecule. Urethane composition. (2. Urethane composition 10 according to claim (1)
0 parts by weight, plus 10 parts by weight of ionizing radiation-curable monomer
- 100 parts by weight of an ionizing radiation-curable urethane composition.