JP2014231563A - Method of producing curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a curable resin composition which enables production of a curable resin composition comprising an unsaturated urethane oligomer and a (meth)acrylic monomer greatly different in viscosity, mixed uniformly, with excellent mass productivity.SOLUTION: A method of producing a curable resin composition includes a step of reacting a polyol (A1) with a polyisocyanate (A2) in a reactor 1 provided with a reaction vessel 10 and stirring means 20 which is arranged in the reaction vessel 10 and has a helical ribbon blade 24 and a lower paddle blade 26 to obtain an isocyanate-terminal urethane prepolymer (A), a step of adding a (meth)acryl monomer (B) having an active hydrogen group to the reaction vessel 1 to react with the isocyanate-terminal urethane polymer (A) so as to obtain an unsaturated urethane oligomer (I) and a step of adding a (meth)acryl monomer (II) to the reaction vessel and mixing.

Description

  The present invention relates to a method for producing a curable resin composition.

  In laminated glass used for windshields for automobiles, window glass for buildings (safety glass, security glass, etc.) and the like, a transparent laminate in which a pair of transparent substrates are bonded together with a cured resin layer is widely used. It has also been proposed that the transparent laminate is used for display applications. Examples of the curable resin composition used for forming the cured resin layer include, for example, an unsaturated urethane oligomer having a photocurable unsaturated group such as an acryloyloxy group and a methacryloyloxy group, and an acrylic monomer or a methacrylic monomer. (Hereinafter, these are collectively referred to as “(meth) acrylic monomers”) and curable resin compositions are known (Patent Document 1).

  For example, the curable resin composition is obtained by reacting a polyol with a polyisocyanate to obtain an isocyanate group-terminated urethane prepolymer whose end group is an isocyanate group, and then adding a hydroxyl group to the isocyanate group-terminated urethane prepolymer. An unsaturated urethane oligomer is obtained by reacting the (meth) acrylic monomer to be produced, and finally the (meth) acrylic monomer is mixed.

International Publication No. 2010/134547

  However, unsaturated urethane oligomers are extremely high in viscosity and greatly different from (meth) acrylic monomers. Therefore, the unsaturated urethane oligomer and the (meth) acrylic monomer can be sufficiently uniformly mixed with a small scale, but it is difficult to uniformly mix them with a large scale. From this, it is difficult to obtain a curable resin composition containing an unsaturated urethane oligomer and a (meth) acrylic monomer with sufficient mass productivity.

  The present invention provides a method for producing a curable resin composition, which is capable of producing a curable resin composition in which an unsaturated urethane oligomer and a (meth) acryl monomer having greatly different viscosities are well mixed, with excellent mass productivity. .

The present invention employs the following configuration in order to solve the above problems.
[1] A method for producing a curable resin composition comprising unsaturated urethane oligomer (I) and (meth) acrylic monomer (II), comprising the following steps (1) to (3).
Step (1): Polyol (A1) and polyisocyanate by a reaction apparatus having a reaction vessel and a stirring device having a helical ribbon blade and a paddle blade located in the lower part of the helical ribbon blade provided in the reaction vessel. (A2) is stirred and reacted to obtain an isocyanate group-terminated urethane prepolymer (A).
Step (2): The (meth) acrylic monomer (B) having an active hydrogen group is added to the reactor and reacted with the isocyanate group-terminated urethane prepolymer (A) to obtain an unsaturated urethane oligomer (I). Process.
Step (3): A step of adding (meth) acrylic monomer (II) to the reaction vessel and mixing with the unsaturated urethane oligomer (I).
[2] The method for producing a curable resin composition according to [1], wherein a curable resin composition having a viscosity at 25 ° C. of 10 to 3,000 Pa · s is produced.
[3] The method for producing a curable resin composition according to [1] or [2], wherein the (meth) acrylic monomer (II) is a (meth) acrylic monomer (II-1) having an active hydrogen group. .
[4] The viscosity of the unsaturated urethane oligomer (I) at 60 ° C is 300 to 1,000 Pa · s, and the viscosity of the (meth) acrylic monomer (II) at 25 ° C is 0.01 to 200 mPa · s. [1] A method for producing a curable resin composition according to any one of [3].
[5] The curable resin composition according to any one of [1] to [4], wherein a ratio d / D of the blade diameter d of the helical ribbon blade to the diameter D of the reaction vessel is 0.70 to 0.97. Manufacturing method.

  According to the method for producing a curable resin composition of the present invention, a low-viscosity raw material in the initial stage of reaction, an unsaturated urethane oligomer that has become highly viscous as the reaction proceeds can be well stirred, and a high-viscosity unsaturated urethane A curable resin composition in which (meth) acrylic monomers having greatly different viscosities are mixed well with oligomers can be produced with excellent mass productivity.

It is the schematic block diagram which showed an example of the reaction apparatus used for the manufacturing method of the curable resin composition of this invention. It is the schematic block diagram which showed the other example of the reaction apparatus used for the manufacturing method of the curable resin composition of this invention. It is the figure which showed the viscosity change of the process (2) in Example 1 and Comparative Example 1. FIG.

[Reactor]
An example of a reaction apparatus used in the method for producing a curable resin composition of the present invention is shown in FIG.
As shown in FIG. 1, the reaction apparatus 1 of the present embodiment includes a reaction vessel 10 and stirring means 20 provided in the reaction vessel 10.
The reaction vessel 10 is a vessel having a circular bottom surface portion and a cylindrical side wall portion.
The stirring means 20 includes a stirring shaft 22 extending in the vertical direction, two helical ribbon blades 24 and 24 attached to the stirring shaft 22, a lower paddle blade 26 provided below the helical ribbon blades 24 and 24, have.

  In this example, two helical ribbon wings 24 are provided, but a helical ribbon wing consisting of only one or three or more may be installed. In the present invention, it is preferable to provide two or one helical ribbon blades.

  The upper end portion of the helical ribbon blade 24 is fixed to the stirring shaft 22 via the support rod 28. Further, as a countermeasure against shaking of the helical ribbon blade due to scale-up of the reactor, the helical ribbon blade 24 is fixed to the stirring shaft 22 at a plurality of points, for example, by fixing the lower end portion of the helical ribbon blade 24 via a support rod. May be.

  The helical ribbon blade 24 is spirally installed along the inner wall surface of the reaction vessel 10 such that the belt-like metal flat plate has a clearance from the inner wall surface of the reaction vessel 10. The rotation of the helical ribbon blade 24 causes a fluid flow near the wall of the reaction vessel 10.

The lower paddle blade 26 is attached to the stirring shaft 22 at the lower portion of the helical ribbon blade 24. The lower paddle blade 26 may be attached to the lower end portion of the helical ribbon blade 24.
Due to the rotation of the helical ribbon blade 24, the highly viscous fluid in the vicinity of the reaction vessel wall is forced to flow upwards of the vessel to improve the heat transfer rate, and further, the rotation of the lower paddle blade 26 causes a fluid retention portion at the lower portion of the vessel. It becomes difficult to occur.

The lower paddle blade 26 may be provided so as to be parallel to the stirring shaft 22, that is, to be inclined at 0 ° with respect to the stirring shaft 22, or may be provided to be inclined with respect to the stirring shaft 22. The lower paddle blades 26 are preferably inclined so that the fluid is forced to flow upwardly by the rotation.
The shape of the lower paddle blade 26 is substantially semicircular in this example, but is not particularly limited, and may be a rectangle or the like.

In Figure 1, D is the diameter of the reaction vessel 10, d is the impeller diameter in the helical ribbon impellers 24, h is blade height, d ₁ of the helical ribbon blade 24 showing the blade length of the lower paddle blades. Moreover, blade pitch of the helical ribbon blade 24, i.e. one turn of the height of the helix of the helical ribbon blade 24 and h _1.

The ratio d / D of the blade diameter d of the helical ribbon blade 24 to the diameter D of the reaction vessel 10 is preferably 0.70 to 0.97. When the ratio D / d is within the above range, the stirring power can be further reduced, and further, uniform mixing is facilitated, and a good heat transfer effect is easily obtained.
The ratio d ₁ / D of the blade length d ₁ of the lower paddle blade to the diameter D of the reaction vessel 10 is preferably 0.70 to 0.98. When the ratio ratio d ₁ / D is within the above range, mixing at the lower part of the reaction vessel 10 becomes better, and a fluid retention portion is less likely to occur.
The ratio h ₁ / h of the blade pitch h ₁ (height of one turn of the spiral) to the blade height h of the helical ribbon blade 24 may be 1 or more and less than 1, and is preferably 0.5 to 2.

  The material of the reaction vessel 10 is not particularly limited, and commonly used materials such as stainless steel, glass, fiber reinforced plastic (FRP) and ceramics can be used. The surface of the reaction vessel 10 may be coated with a fluororesin or the like. Stainless steel is particularly preferable as the material of the reaction vessel 10.

[Method for producing curable resin composition]
Hereinafter, the manufacturing method using the said reaction apparatus 1 is demonstrated as an example of the manufacturing method of the curable resin composition of this invention.
The manufacturing method of the curable resin composition of this embodiment has the following process (1)-(3).
Step (1): The polyol (A1) and the polyisocyanate (A2) are stirred and reacted by the reaction apparatus 1 to react with the isocyanate group-terminated urethane prepolymer (A) (hereinafter referred to as “prepolymer (A)”). Obtaining.
Step (2): A step of adding the (meth) acrylic monomer (B) having an active hydrogen group to the reaction apparatus 1 and reacting with the prepolymer (A) to obtain the oligomer (I).
Step (3): A step of adding (meth) acrylic monomer (II) to reaction vessel 10 and mixing with said oligomer (I).

(Process (1))
The polyol (A1) and the polyisocyanate (A2) are placed in the reaction vessel 10 of the reaction apparatus 1, and the prepolymer (A) is obtained by reacting them with an index exceeding 100 while being stirred by the stirring means 20.
The index is a value obtained by dividing the number of moles of isocyanate group of polyisocyanate (A2) by the number of moles of hydroxyl group of polyol (A1) and multiplying by 100.

30-90 degreeC is preferable and, as for the reaction temperature in a process (1), 50-80 degreeC is more preferable.
In the present invention, the order in which the polyol (A1) and the polyisocyanate (A2) are charged into the reaction vessel 10 may be either, but it is preferable to charge the polyisocyanate (A2) first.

Examples of the polyol (A1) include polyoxyalkylene polyols obtained by reacting a monoepoxide (a12) with an initiator (a11) having active hydrogen. The polyoxyalkylene polyol has a polyoxyalkylene chain. The polyol (A1) is preferably a polyoxyalkylene polyol obtained by reacting the initiator (a11) with the monoepoxide (a12) in the presence of the catalyst (a13).
A polyol (A1) may be used individually by 1 type, and may use 2 or more types together.

The active hydrogen means an active hydrogen atom with which monoepoxide can react, such as a hydrogen atom of a hydroxyl group or a hydrogen atom of an amino group. As the active hydrogen, a hydrogen atom of a hydroxyl group is preferable.
As the initiator (a11), a polyhydroxy compound having an average number of hydroxyl groups of 2 to 4 is preferable, and a polyhydroxy compound having an average number of hydroxyl groups of 2 to 3 is more preferable.

Examples of the initiator (a11) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimerolpropane, pentaerythritol, and these Examples thereof include polyoxyalkylene polyols having a lower molecular weight than polyol (A1) obtained by reacting alkylene oxide.
An initiator (a11) may be used individually by 1 type, and may use 2 or more types together.

Monoepoxide (a12) is a compound having one epoxy ring.
Examples of the monoepoxide (a12) include ethylene oxide (hereinafter referred to as “EO”), propylene oxide (hereinafter referred to as “PO”), 1,2-butylene oxide, 2,3-butylene oxide, and styrene. Examples include alkylene oxides such as oxide, glycidyl ether, glycidyl ester, and the like. Of these, alkylene oxide is preferable, and EO and PO are more preferable.
Monoepoxide (a12) may be used individually by 1 type, and may use 2 or more types together.

Examples of the catalyst (a13) include diethyl zinc, iron chloride, metal porphyrin, double metal cyanide complex, cesium compound, alkali (earth) metal compound and the like. Among these, an alkali metal compound catalyst or a double metal cyanide complex is preferable, and a double metal cyanide complex is particularly preferable for producing a polyol (A1) having a low hydroxyl value and a low degree of unsaturation.
A catalyst (a13) may be used individually by 1 type, and may use 2 or more types together.

2-4 are preferable and, as for the average number of hydroxyl groups per molecule of a polyol (A1), 2-3 are more preferable. If the average number of hydroxyl groups per molecule of the polyol (A1) is 2 to 4, an oligomer (I) having an average number of (meth) acryloyloxy groups per molecule of 2 to 4 can be easily obtained.
When the initiator (a11) is one kind, the average number of hydroxyl groups per molecule of the polyol (A1) is the number of active hydrogens per molecule of the initiator (a11), and the initiator (a11) has two kinds. In the case of a mixture, it is an average value of the number of active hydrogens per molecule of the initiator (a11).

The hydroxyl value of the polyol (A1) is preferably 3.8 to 56.1 mgKOH / g, more preferably 5.6 to 37.4 mgKOH / g, and particularly preferably 9.3 to 28 mgKOH / g. If the hydroxyl value of a polyol (A1) is more than a lower limit, the intensity | strength of hardened | cured material will become favorable. Moreover, it can suppress that a viscosity becomes high too much because the molecular weight of a polyol (A1) becomes large, and the workability | operativity at the time of manufacture of a prepolymer (A) becomes favorable. When the hydroxyl value of the polyol (A1) is not more than the upper limit value, a cured product that is flexible and suppresses color unevenness is formed at a high curing rate.
The hydroxyl value of the polyol (A1) is a value measured according to JIS K1557-1 (2007 edition).
A polyol (A1) may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyisocyanate (A2) include alicyclic polyisocyanates, aliphatic polyisocyanates having two or more average isocyanate groups per molecule, and modified polyisocyanates obtained by modifying these. The aliphatic polyisocyanate may have an aromatic ring. An aromatic polyisocyanate having an isocyanate group bonded to an aromatic ring is preferably not used because it is highly likely to cause yellowing of the cured resin.
2-4 are preferable and, as for the average number of isocyanate groups per molecule of polyisocyanate (A2), 2 is especially preferable. That is, as the polyisocyanate (A2), diisocyanate is preferable.
Polyisocyanate (A2) may be used individually by 1 type, and may use 2 or more types together.

  Specific examples of the polyisocyanate (A2) include diisocyanates such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and xylene diisocyanate, prepolymer modified products, nurate modified products, urea modified products, and carbodiimide modified products of the diisocyanate. It is done. Of these, isophorone diisocyanate and hexamethylene diisocyanate are preferable.

  The index when the polyol (A1) and the polyisocyanate (A2) are reacted is more than 100, the strength of the cured product is good, and in order to prevent rapid thickening during the urethanization reaction, the index is 102 or more. Preferably, 103 or more is more preferable. In addition, the index is preferably 200 or less, and more preferably 150 or less, because a cured product that is more flexible and has suppressed color unevenness can be obtained.

For the reaction of the polyol (A1) and the polyisocyanate (A2), it is preferable to use a urethanization catalyst.
Examples of the urethanization catalyst include cobalt naphthenate, zinc naphthenate, zinc 2-ethylhexanoate, dibutyltin dilaurate, tin 2-ethylhexanoate, triethylamine, 1,4-diabicyclo [2.2.2] octane, and the like. It is done.
Further, in the step (1), it has a (meth) acryloyloxy group, a reaction between the polyol (A1) and the polyisocyanate (A2), and a prepolymer (A) and an active hydrogen group in the step (2) ( Diluted monomers that do not participate in the reaction with the (meth) acrylic monomer (B) may be used. Examples of the dilution monomer include isobornyl acrylate, lauryl acrylate, stearyl acrylate, and the like.

The viscosity at 60 ° C. of the prepolymer (A) obtained in the step (1) is preferably 10 to 1000 Pa · s, more preferably 20 to 800 Pa · s.
The viscosity of the prepolymer (A) is a value measured using an E-type viscometer.

(Process (2))
(Meth) acrylic monomer (B) having an active hydrogen group is added to reaction vessel 10 and reacted with prepolymer (A) obtained in step (1) while stirring to obtain oligomer (I). . The active hydrogen group is a group having an active hydrogen atom that can react with the isocyanate group of the prepolymer (A). As the active hydrogen group, a hydroxyl group is preferable.
By reacting the prepolymer (A) and the (meth) acrylic monomer (B), the isocyanate group at the end of the prepolymer (A) and the active hydrogen group of the (meth) acrylic monomer (B) are reacted and bonded. , An oligomer (I) having a (meth) acryloyloxy group is obtained.

  By using the reactor 1, the prepolymer (A) and the (meth) acrylic monomer (B) are better than when using a reactor having only a helical ribbon blade or a reactor having only a paddle blade. The reaction proceeds rapidly.

  30-90 degreeC is preferable and, as for the reaction temperature in a process (2), 50-75 degreeC is more preferable.

  The ratio of the prepolymer (A) and the (meth) acrylic monomer (B) used for the reaction is the molar ratio of the isocyanate group of the prepolymer (A): the active hydrogen group of the (meth) acrylic monomer (B) is 1 : 1 to 1: 1.5 is preferable, and 1: 1 to 1: 1.2 is more preferable.

The (meth) acrylic monomer (B) may have one (meth) acryloyloxy group in one molecule, or may have two or more. Moreover, the (meth) acryl monomer (B) may have one active hydrogen group in one molecule, or may have two or more.
The (meth) acrylic monomer (B) is preferably a hydroxyalkyl (meth) acrylate having one (meth) acryloyloxy group and one hydroxyl group in one molecule. Moreover, as a (meth) acryl monomer (B), the hydroxyalkyl (meth) acrylate which has a C2-C8 hydroxyalkyl group is more preferable, and the hydroxyalkyl (C2-C4 hydroxyalkyl group which has a hydroxyalkyl group ( Particularly preferred is (meth) acrylate.

Examples of the (meth) acrylic monomer (B) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate and the like. Of these, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferable, and 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate are particularly preferable.
The (meth) acrylic monomer (B) may be used alone or in combination of two or more.

In the step (2), a polymerization inhibitor may be used as necessary.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butylhydroquinone, o-nitrotoluene and the like.
As for the usage-amount of a polymerization inhibitor, 50-5000 mass ppm is preferable with respect to the total mass of the (meth) acryl monomer (B) used for reaction.

The viscosity of the oligomer (I) obtained in the step (2) at 60 ° C. is preferably 300 to 1,000 Pa · s, and more preferably 400 to 900 Pa · s.
The viscosity is a value measured using an E-type viscometer (RE-85U, manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS K1557-5 (2007).

  The number average molecular weight of the unsaturated urethane oligomer (I) obtained in the step (2) is preferably 20,000 to 100,000, more preferably 30,000 to 70,000. The number average molecular weight is a value obtained by using gel as a calibration curve by gel permeation chromatography (GPC).

(Process (3))
(Meth) acrylic monomer (II) is added into reaction vessel 10 and stirred by stirring means 20 to be mixed with oligomer (I) obtained in step (2) to obtain a curable resin composition. The (meth) acrylic monomer (II) may be added and mixed at a time, or may be added and mixed in a plurality of times.

  The viscosity of the (meth) acrylic monomer (II) is generally 200 mPa · s or less at 25 ° C. The upper limit of the viscosity of the (meth) acrylic monomer (II) in the present invention is preferably 200 mPa · s at 25 ° C., more preferably 100 mP · s, and particularly preferably 25 mPa · s. Although there is no particular lower limit, 0.01 mPa · s is preferred at 25 ° C., 0.1 mPa · s is more preferred, and 0.5 mPa · s is particularly preferred.

  Since the oligomer (I) has a very high viscosity, the viscosity of the oligomer (I) and the (meth) acrylic monomer (II) is greatly different. In the present embodiment, the stirring means 20 includes the helical ribbon blade 24 and the lower paddle blade 26 provided at the lower portion of the helical ribbon blade 24, so that the oligomers (I) and (meta) whose viscosity is increased. Acrylic monomer (II) can be mixed uniformly. The factors for obtaining this effect are considered as follows.

The mixing by the helical ribbon blade proceeds by raising the solution to be mixed by rotation to cause upward flow, or pushing down the solution to be mixed by rotation to cause downward flow. However, when the viscosity of the solution to be mixed is low, it is difficult to cause upward flow or downward flow, and uniform mixing becomes difficult. Therefore, with only the helical ribbon blade, the low-viscosity (meth) acrylic monomer (II) is difficult to flow in the container, and it is difficult to uniformly mix the oligomer (I) and the (meth) acrylic monomer (II). The paddle blade is suitable for mixing low-viscosity solutions, but the higher the viscosity of the solution to be mixed, the more effective the stirring is in the vicinity of the paddle blade, making uniform mixing difficult. Become. Therefore, with the paddle blade alone, it is difficult for the oligomer (I) having extremely high viscosity to flow as a whole in the container, and it is difficult to uniformly mix the oligomer (I) and the (meth) acrylic monomer (II).
On the other hand, when the reactor 1 is used, the oligomer (I) and the (meth) acrylic monomer (II) are stirred by the lower paddle blade 26 at the lower part of the reaction vessel 10, and the upward flow is caused by the helical ribbon blade 24. Or since the downward flow is caused, the oligomer (I) and the (meth) acrylic monomer (II) flow throughout the reaction vessel 10, so that they are well mixed.

  The reactor used in the present invention is effective when mixing the oligomer (I) having a viscosity at 60 ° C. of 300 to 1,000 Pa · s and the (meth) acrylic monomer (II), and the viscosity at 60 ° C. is 400. This is particularly effective when the oligomer (I) and (meth) acrylic monomer (II) of up to 900 Pa · s are mixed.

  50-80 degreeC is preferable and the mixing temperature in a process (3) has more preferable 60-75 degreeC.

The direction of rotation of the helical ribbon blade 24 is preferably the direction in which the oligomer (I) and the (meth) acrylic monomer (II) are placed on the helical ribbon blade 24 and sent upward of the reaction vessel 10, that is, the direction causing the upward flow. . In particular, the (meth) acrylic monomer (II) having a low viscosity tends to accumulate in the lower part of the reaction vessel 10, but an upward flow is generated in the reaction vessel 10 by the helical ribbon blades 24. Since the oligomer (I) and the (meth) acrylic monomer (II) can be sufficiently fluidized, the oligomer (I) and the (meth) acrylic monomer (II) can be more uniformly mixed.
In this example, the rotation direction of the right-handed helical ribbon blade 24 is preferably left-handed rotation.

The (meth) acrylic monomer (II) is a monomer having a (meth) acryloyloxy group. The (meth) acrylic monomer (II) may have one (meth) acryloyloxy group in one molecule, or may have two or more.
As the (meth) acrylic monomer (II), a (meth) acrylic monomer (II-1) having an active hydrogen group is preferable. As the active hydrogen group, a hydroxyl group is preferable. The (meth) acrylic monomer (II-1) may have one active hydrogen group in one molecule or two or more.
The (meth) acrylic monomer (II-1) is preferably one having one (meth) acryloyloxy group and one active hydrogen group in one molecule.

  As (meth) acryl monomer (II-1), the same thing as what was mentioned as (meth) acryl monomer (B) is mentioned, for example. Especially, the hydroxyalkyl (meth) acrylate which has a C2-C4 hydroxyalkyl group is preferable, and the hydroxyalkyl (meth) acrylate which has a C2-C4 hydroxyalkyl group is especially preferable.

  Examples of the (meth) acrylic monomer (II-1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. 4-hydroxybutyl (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, and the like. Of these, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferable, and 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate are particularly preferable.

The (meth) acrylic monomer (II) may be a (meth) acrylic monomer that does not have an active hydrogen group.
Examples of the (meth) acrylic monomer having no active hydrogen group include n-lauryl acrylate, n-dodecyl methacrylate, n-octadecyl methacrylate, n-behenyl methacrylate, and the like. Of these, n-dodecyl methacrylate and n-octadecyl methacrylate are preferable.
(Meth) acrylic monomer (II) may be used alone or in combination of two or more.

  The amount of the (meth) acrylic monomer (II) to be mixed with the oligomer (I) is preferably 3 to 150 parts by mass and more preferably 5 to 130 parts by mass with respect to 100 parts by mass of the oligomer (I). If the usage-amount of (meth) acrylic monomer (II) is more than a lower limit, it will be excellent in the adhesiveness to a base material. If the amount of (meth) acrylic monomer (II) used is less than or equal to the upper limit value, the shrinkage during curing is small and preferable.

  It is preferable that a photopolymerization initiator (III) is further added to the curable resin composition. That is, the curable resin composition of the present invention is preferably a photocurable resin composition in which a curing reaction proceeds by light irradiation. The blending of the photopolymerization initiator (III) may be performed before mixing the (meth) acrylic monomer (II) or may be performed simultaneously with the mixing of the (meth) acrylic monomer (II). You may carry out after mixing monomer (II).

  As the photopolymerization initiator (III), those which are excited by irradiation with visible light or ultraviolet light (wavelength 300 to 400 nm) and are activated to promote the curing reaction are preferable. Specific examples include benzoin ether photopolymerization initiators, α-hydroxyalkylphenone photopolymerization initiators, and acylphosphine oxide photopolymerization initiators.

Specific examples of the photopolymerization initiator (III) include benzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, acetophenone, 3-methylacetophenone, benzoyl, benzoin isobutyl ether, benzoin Isopropyl ether, benzoin ethyl ether, anthraquinone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2- Examples thereof include hydroxy-2-methyl-1-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like. Among them, 1-hydroxycyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, bis (2,4,6-trimethyl) Acylphosphine oxide photopolymerization initiators such as benzoyl) -phenylphosphine oxide are preferred, and 1-hydroxycyclohexyl phenyl ketone, bis (2, 4,6-trimethylbenzoyl) -phenylphosphine oxide is particularly preferred.
The photopolymerization initiator (III) may be used alone or in combination of two or more.

  Moreover, you may mix | blend other components (IV) other than oligomer (I), (meth) acryl monomer (II), and photoinitiator (III) with curable resin composition. The other component (IV) may be blended before mixing the (meth) acrylic monomer (II), or may be performed simultaneously with the mixing of the (meth) acrylic monomer (II). You may carry out after mixing (II).

Examples of the other component (IV) include other oligomers other than the oligomer (I), additives, curing agents that generate radicals by heat, solvents, and the like.
Other oligomers include, for example, poly (meth) acrylate obtained by reacting (meth) acrylic acid with polyoxyalkylene polyol, poly (meth) acrylate obtained by reacting polyester polyol with (meth) acrylic acid, etc. Is mentioned.
Moreover, you may add a various additive to a curable resin composition according to a use. Examples of the additives include ultraviolet absorbers (benzotriazoles, hydroxyphenyltriazines, etc.), light stabilizers (hindered amines, etc.), pigments, dyes, metal oxide fine particles, fillers, and the like.
When a curing agent that generates radicals by heat is blended, the photopolymerization initiator (III) is not blended.

  In this invention, when using for manufacture of the transparent laminated body mentioned later especially, it is more preferable that oligomer (I), (meth) acryl monomer (II), and photoinitiator (III) are included. The curable resin composition of the present invention may be a composition composed only of the oligomer (I) and the (meth) acrylic monomer (II).

  20-95 mass% is preferable and, as for content of oligomer (I) in curable resin composition (100 mass%), 40-90 mass% is more preferable. If content of oligomer (I) is more than a lower limit, even if hardened | cured material is exposed to high temperature, it is hard to deform | transform. If content of oligomer (I) is below an upper limit, hardened | cured material will become difficult to become weak.

  The content of the (meth) acrylic monomer (II) in the curable resin composition (100% by mass) is preferably 5 to 65% by mass, and more preferably 10 to 50% by mass. If content of (meth) acrylic monomer (II) is more than a lower limit, when a transparent laminated body is manufactured, the adhesiveness of a cured resin layer and a transparent substrate and tear resistance will become favorable. If the content of the (meth) acrylic monomer (II) is not more than the upper limit value, the shrinkage during curing is small and preferable.

When mix | blending photoinitiator (III) with curable resin composition, content of photoinitiator (III) in curable resin composition is 0.00 with respect to 100 mass parts of oligomer (I). 01-10 mass parts is preferable, and 0.1-2.5 mass parts is more preferable.
When the other component (IV) is added to the curable resin composition, the content of the other component (IV) in the curable resin composition (100% by mass) is preferably 10% by mass or less. The mass% or less is more preferable.

The viscosity at 25 ° C. of the curable resin composition obtained by the production method of the present invention is preferably 10 to 3,000 Pa · s, more preferably 15 to 2,000 Pa · s, and particularly preferably 15 to 1,800 Pa · s. preferable. If the said viscosity is below an upper limit, sufficient fluidity | liquidity will be obtained for curable resin composition, and it will be hard to produce a bubble in curable resin composition. If the viscosity is equal to or higher than the lower limit, it is not necessary to use a large amount of a low molecular weight monomer such as (meth) acrylic monomer (II) in order to lower the viscosity, so that the physical properties of the cured product are hardly lowered. .
The viscosity is a value measured using an E-type viscometer in accordance with JIS K1557-5 (2007).

  The use of the curable resin composition obtained by the production method of the present invention is not particularly limited. For example, a cured resin layer for bonding a pair of transparent substrates in a laminated glass such as a windshield of an automobile and a window glass of a building. Can be used to form

  According to the method for producing a curable resin composition of the present invention described above, in order to use a reactor equipped with a stirring means having a helical ribbon blade and paddle blades provided above and below the helical ribbon blade, In the step (3), the oligomer (I) and the (meth) acrylic monomer (II) having greatly different viscosities can be mixed well, and a curable resin composition can be produced with excellent mass productivity. Moreover, also in a process (2), since a prepolymer (A) and a (meth) acryl monomer (B) can be mixed favorably, they can be made to react rapidly.

[Other Embodiments]
The manufacturing method of the curable resin composition of this invention is not limited to an above described method.
For example, the method for producing the curable resin composition of the present invention may be a method using a reaction apparatus other than the reaction apparatus 1. Specifically, for example, a method using the reaction apparatus 2 illustrated in FIG. 2 may be used. The same parts in FIG. 2 as those in FIG.
In the reactor 2, in addition to the helical ribbon blade 24 and the lower paddle blade 26, the stirring pad 20 </ b> A has a central paddle blade 30 attached to the stirring shaft 22 inside the central portion in the height direction of the helical ribbon blade 24. It is the same as the reaction apparatus 1 except having.
The central paddle wing 30 may be attached to the helical ribbon wing 24.

  In the stirring means 20A having the helical ribbon blade 24, the lower paddle blade 26, and the center paddle blade 30, the helical ribbon blade 24 forcibly causes the highly viscous fluid in the vicinity of the inner wall of the reaction vessel 10 to flow upwardly to increase the heat transfer rate. In addition, the fluid in the container is uniformly mixed and dispersed by the central paddle blade 30, and at the same time, the lower paddle blade 26 suppresses the occurrence of a fluid retention portion in the lower portion of the container.

The central paddle blade 30 may be provided so as to be parallel to the stirring shaft 22, that is, to be inclined at 0 ° with respect to the stirring shaft 22, or may be provided to be inclined with respect to the stirring shaft 22. In the reactor 2, the central paddle blade 30 is inclined so that the fluid is forced to flow downward by the rotation, and the lower paddle blade is inclined to force the fluid to flow upward by the rotation. 26 is preferably provided.
The shape of the central paddle blade 30 is trapezoidal in this example, but is not particularly limited, and may be a rectangle or the like.

In FIG. 2, d ₂ indicates the blade length of the central paddle blade 30.
The ratio d ₂ / D of the blade length d ₂ of the central paddle blade 30 to the diameter D of the reaction vessel 10 is preferably 0.4 to 0.65. If the ratio d ₂ / D is within the above range, the stirring power becomes smaller and uniform mixing becomes easier.

In addition to the helical ribbon wing and the lower paddle wing, it is preferable to use a reactor having a stirring means having an upper paddle wing above the helical ribbon wing. If the upper paddle blade and the lower paddle blade are provided above and below the helical ribbon blade, the oligomer (I) and the (meth) acrylic monomer (II) can be mixed more efficiently.
Moreover, you may use the reaction apparatus which has the helical ribbon blade | wing wound up one or more turns. The helical ribbon wing is preferably wound half or more times. Alternatively, a reaction device having a left-handed helical ribbon blade may be used.

Moreover, you may use the reactor which attaches a scraper along the outer edge part of a helical ribbon blade | wing, and can stir while scraping off the compound adhering to the inner wall face of a reaction container with this scraper.
In this case, the ratio of the diameter of the helical ribbon blade attached with the scraper to the diameter of the reaction vessel is preferably 1.01 to 1.05. When the ratio is within the above range, the effect of scraping off the compound adhering to the inner wall surface of the reaction vessel by the scraper can be sufficiently obtained.
The ratio of the length from the outer end of the scraper to the inner end of the helical ribbon blade relative to the diameter of the reaction vessel, that is, the ratio of the width of the helical ribbon blade attached with the scraper is preferably 0.04 to 0.16. If the ratio is within the above range, the stirring power becomes smaller, further uniform mixing is facilitated, and a good heat transfer effect is easily obtained.

Moreover, you may use the reaction apparatus which has a stirring means which has a mechanism which can adjust the rotational speed of a helical ribbon blade | wing and the rotational speed of a lower paddle blade to different speeds.
Further, in the reaction apparatus used in the present invention, the paddle blade provided at the lower portion of the helical ribbon blade is not limited to the form provided at the lower end of the helical ribbon blade, and is within the range not impairing the effect of the present invention. You may provide slightly above the lower end of a helical ribbon wing | blade. Moreover, when providing in the lower part of a helical ribbon wing | blade, it may be in contact with the lower end of a helical ribbon wing | blade, and it is preferable that it is provided in contact.
Moreover, the manufacturing method of the curable resin composition of this invention may use the reaction apparatus with which the paddle blade is integrated and fixed with the stirring shaft. The inclination angle of the paddle wing provided at the lower portion of the helical ribbon wing may be different from the inclination angle of the lower end portion of the helical ribbon wing.
Further, the shape of the reaction vessel of the reaction apparatus used in the present invention may be a shape other than the reaction vessel 10.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description.
In this example, the reactor 1 illustrated in FIG. 1 was used. Table 1 shows dimensions and the like of each part in the reactor 1.

[Measurement method of isocyanate group content]
It was measured by a titration method in accordance with JIS K7301.

[Gel permeation chromatography (GPC) measurement conditions]
Model used: HLC-8220GPC (manufactured by Tosoh Corporation),
Data processing device: GPC-8020 model II (manufactured by Tosoh Corporation),
Column used: TSK-GEL SuperMultipore HZ 4000 × 2, 2500 × 2 (manufactured by Tosoh Corporation),
Column temperature: 40 ° C
Detector: differential refractometer (RI),
Solvent: tetrahydrofuran,
Flow rate: 0.35 mL / min,
Sample concentration: 0.05% by mass
Injection volume: 20 μL,
Standard sample for preparing a calibration curve: polystyrene ([Easical] PS-2 [Polystyrene Standards], manufactured by Polymer Laboratories).

[Viscosity measurement]
The viscosity was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE-85U). However, when the viscosity was 100 Pa · s or less, 1 ° 34 ′ × R24 was used as the rotor, and when the viscosity exceeded 100 Pa · s, 3 ° × R9.7 was used as the rotor.

[Example 1]
The following method was used to produce a curable resin composition having a viscosity at 25 ° C. of 1,400 to 1,600 Pa · s as a target product.
(Process (1))
In the reaction vessel 10 of the reactor 1, a polyoxyalkylene polyol having a number average molecular weight of 4,000 as the polyol (A1) (average number of hydroxyl groups: 2, hydroxyl value: 28.1 mgKOH / g, viscosity (25 ° C.): 900 mPa · s. 51.34 kg of s), 2.33 kg of hexamethylene diisocyanate (HDI, viscosity (25 ° C.): 3 mPa · s) as polyisocyanate (A2), and isobornyl acrylate (IBXA, viscosity (25 ° C.) as a dilution monomer : 8 mPa · s), 23.16 kg, and 0.83 g of dioctyltin dilaurate (U500: manufactured by Nitto Kasei Co., Ltd.) as the urethanization catalyst were charged, and the rotational speed of the helical ribbon blade 24 and the lower paddle blade 26 was adjusted in a nitrogen atmosphere. React at 60 rpm for about 25 hours at 80 ° C. To give a prepolymer A-1. The viscosity (60 ° C.) of the resulting isocyanate group-terminated prepolymer A-1 was 480 Pa · s.
(Process (2))
Next, in the reaction vessel 10, 3.1 g of 2-hydroxyethyl acrylate as the (meth) acrylic monomer (B), 16.1 g of 2,5-di-tert-butylhydroquinone as the polymerization inhibitor, and dibutyltin dilaurate (U100: manufactured by Nitto Kasei Co., Ltd.) was charged and reacted with the isocyanate group-terminated prepolymer A-1 at 70 ° C. under a dry air atmosphere at a rotational speed of the helical ribbon blade 24 and the lower paddle blade 26 of 50 rpm. .
Every 1 hour, from the upper part of the reaction vessel 10 (a place with a height of about 5 cm from the liquid level), the middle part (a place with a height of about 20 cm from the liquid level), and the lower part (the sample outlet at the bottom of the reactor) Sampling was performed, and the isocyanate group content and viscosity were measured, respectively. When it was confirmed that the isocyanate group disappeared, the reaction was terminated, and an unsaturated urethane oligomer I-1 was obtained. The reaction time was 4 hours.
It was 53,000 when the number average molecular weight Mn of the obtained unsaturated urethane oligomer I-1 was measured by GPC. Moreover, the viscosity (60 degreeC) of the obtained unsaturated urethane oligomer I-1 was 750 Pa.s.
(Process (3))
Next, 148 g of 2-hydroxybutyl acrylate (viscosity (25 ° C.): 10 mPa · s) as (meth) acrylic monomer (II) was added in three portions to the reaction vessel 10, and the helical ribbon blade 24 and the lower part were added. The rotational speed of the paddle blade 26 was 60 rpm, and the mixture was stirred at 70 ° C. for 4 hours for a total of 12 hours.
After mixing, 15 kg of the obtained curable resin composition was filled into cans, and the viscosity at 25 ° C. of the curable resin composition sampled for each can was measured.

[Comparative Example 1]
A curable resin composition was produced in the same manner as in Example 1 except that the same reaction apparatus as the reaction apparatus 1 was used except that the helical ribbon blade 24 was not provided.
About Example 1 and Comparative Example 1, the viscosity change in step (2) is shown in FIG. 3, the reaction time in step (2), the maximum value, the minimum value, and the average value of the viscosity of each sample sampled after mixing in step (3). The yield is shown in Table 2. Yield was calculated as yield = [number of cans of target viscosity × 15 (kg) / charged amount (kg)] × 100.

  As shown in FIG. 3, in Example 1 using the reaction apparatus 1, in the step (2), as compared with Comparative Example 1 using a reaction apparatus that does not have the helical ribbon blade 24, the entire reaction vessel 1 is used. The prepolymer (A) and the (meth) acrylic monomer (B) were easily mixed uniformly, and the reaction proceeded quickly. Moreover, as shown in Table 2, the curable resin composition obtained in the step (3) of Example 1 was compared with the curable resin composition of Comparative Example 1 and was sampled for each can. The viscosity of the product became more uniform and the yield was high.

  DESCRIPTION OF SYMBOLS 1, 2 ... Reaction apparatus, 10 ... Reaction container, 20 ... Stirring means, 22 ... Stirring shaft, 24 ... Helical ribbon blade, 26 ... Lower paddle blade.

Claims (5)

The manufacturing method of curable resin composition containing unsaturated urethane oligomer (I) and (meth) acryl monomer (II) which has following process (1)-(3).
Step (1): Polyol (A1) and polyisocyanate by a reaction apparatus having a reaction vessel and a stirring device having a helical ribbon blade and a paddle blade located in the lower part of the helical ribbon blade provided in the reaction vessel. (A2) is stirred and reacted to obtain an isocyanate group-terminated urethane prepolymer (A).
Step (2): The (meth) acrylic monomer (B) having an active hydrogen group is added to the reactor and reacted with the isocyanate group-terminated urethane prepolymer (A) to obtain an unsaturated urethane oligomer (I). Process.
Step (3): A step of adding (meth) acrylic monomer (II) to the reaction vessel and mixing with the unsaturated urethane oligomer (I).   The manufacturing method of the curable resin composition of Claim 1 which manufactures the curable resin composition whose viscosity in 25 degreeC is 10-3,000 Pa.s.   The method for producing a curable resin composition according to claim 1 or 2, wherein the (meth) acrylic monomer (II) is a (meth) acrylic monomer (II-1) having an active hydrogen group.   The viscosity of the unsaturated urethane oligomer (I) at 60 ° C is 300 to 1,000 Pa · s, and the viscosity of the (meth) acrylic monomer (II) at 25 ° C is 0.01 to 200 mPa · s. The manufacturing method of curable resin composition as described in any one of -3.   The production of the curable resin composition according to any one of claims 1 to 4, wherein a ratio d / D of the blade diameter d of the helical ribbon blade to the diameter D of the reaction vessel is 0.70 to 0.97. Method.

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