JP2013249455A - Urethane (meth)acrylate and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable polycarbonate diol-starting urethane (meth)acrylate which is excellent in all physical properties such as adhesiveness, contamination resistance, hydrolysis resistance, chemical resistance, and flexibility, and is further excellent in apparent smoothness after curing, and a mixed composition using the same.SOLUTION: A urethane (meth)acrylate is a reaction product of an isocyanate compound (a) having at least two isocyanate groups, a polycarbonate diol (b) including a terminal hydroxyl, and a hydroxyl-containing (meth)acrylate (c). In a coating film obtained by ultraviolet-curing a mixture including the following components: 20 pts. of trimethylol propane acrylate, 30 pts. of urethane (meth)acrylate (as a solid content), 52 pts. of n-butyl acetate and 2 pts of 1-hydroxycyclohexyl phenyl ketone, no peeling is observed, and the color difference (ΔE) before and after removal of oil-based black ink with isopropyl alcohol is 3 or less.

Description

  The present invention belongs to a urethane (meth) acrylate and a method for producing the same.

Many energy-ray curable resins that have been cured by irradiation with ultraviolet rays and electron beams and thermosetting resins that have been cured by heat have been developed. These are coating materials and molding materials in a broad sense such as paints, inks, adhesives, and adhesives. As widely used.
Among them, urethane (meth) acrylates are manufactured in various types having features such as toughness, chemical resistance, and flexibility depending on the purpose because of the high degree of design freedom due to the variety of constituent materials.
In particular, urethane (meth) acrylate made from polycarbonate diol has various patents as a material that has good hydrolysis resistance, weather resistance, chemical resistance and excellent flexibility due to its structural features. It is introduced by the literature (refer patent documents 1-5).

Japanese Patent Publication 3301447 JP-A-3-247618 JP-A-2005-171154 JP 6-13692 JP 2002-348499 A

However, the polycarbonate raw material urethane (meth) acrylate introduced in those documents did not pay attention to practical physical properties such as durability when used as a coating material. Specifically, when used as a component of a coating composition for mobile phones and mobile computers that are often carried and used by human hands, all problems such as stains, scratches, cracks, and chipping of the coating film are eliminated. It was difficult to solve. Normally, it is necessary to harden the coating with a polyfunctional acrylic monomer in order to make it difficult to get dirt and scratches. Chipping or cracking may occur. If flexibility is provided to solve such a problem, improved resistance to dirt and scratches may be reduced. That is, these are in a contradictory relationship, and the polycarbonate raw material urethane (meth) acrylate as introduced in the above literature can only solve one of the problems, and as a result, the coating film has excellent durability. Was difficult. A coating film with low durability has a drawback in that it is difficult to maintain the appearance immediately after coating, which is called aesthetic appearance, and as a result, the value of a product using the coating is lowered.
In addition, the various documents do not focus on the primary terminal OH ratio of the polycarbonate diol, which is a raw material, and those having a low primary terminal OH ratio may be used as a synthetic raw material. When low polycarbonate diol is used as a raw material for synthesis, the reaction rate with the reaction partner isocyanate becomes slow, making it difficult to control the rate, and the resulting reaction product may not exhibit the desired performance. there were.
On the other hand, when a polycarbonate diol having a primary terminal OH ratio as close to 100% as possible is used as a raw material for urethane (meth) acrylate, there is a problem that the viscosity of the resultant composite becomes very high.

  The present invention is an excellent physical property that serves as an indicator of durability necessary for maintaining aesthetics, such as adhesion, stain resistance, chemical resistance, hydrolysis resistance, flexibility, and wear resistance. In addition, an object of the present invention is to provide a curable polycarbonate diol raw material urethane (meth) acrylate excellent in appearance smoothness after curing, which does not require an excessive dilution solvent, and a method for producing the same. It is to provide a blended composition.

  As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by using a specific polycarbonate diol, and has led to the present invention.

（但し、式中のＲは、炭素数２〜１２の二価の脂肪族又は脂環族炭化水素を表わす。）

［２］ 上記塗膜を８０℃の温水中４時間浸漬させた後でも、クロスカット法で剥離が認められない、［１］に記載のウレタン（メタ）アクリレート。
［３］ ポリカーボネートジオール（ｂ）の１級末端ＯＨ比率が９５．０〜９９．５％である、［１］又は［２］に記載のウレタン（メタ）アクリレート。
［４］ ポリカーボネートジオール（ｂ）の分子量が、９００〜１１００である、［１］から［３］のいずれか一つに記載のウレタン（メタ）アクリレート。
［５］ ウレタン（メタ）アクリレートを得るための反応の際に生じるイソシアネート化合物（ａ）と水酸基含有（メタ）アクリレート（ｃ）との直接付加物の割合が、反応で得られる生成物全体に対して０．１〜１２重量％である、［１］から［４］のいずれか一つに記載のウレタン（メタ）アクリレート。
［６］ ［１］〜［５］のいずれか一つに記載のウレタン（メタ）アクリレートと、それ以外の（メタ）アクリル酸エステルとを含む、配合組成物。
［７］ 更に、重合開始剤を含む、［６］に記載の配合組成物
［８］ 少なくとも２個以上のイソシアネート基を有するイソシアネート化合物（ａ）と、下記一般式（Ａ）で表わされる繰り返し単位及び末端ヒドロキシル基からなり、必須の繰り返し単位として下記式（Ｂ）で表わされる繰り返し単位と下記式（Ｃ）で表わされる繰り返し単位とを含み、下記式（Ｂ）で表わされる繰り返し単位と下記式（Ｃ）で表わされる繰り返し単位の合計が一般式（Ａ）で表わされる繰り返し単位全体の６０〜１００モル％であり、かつ１級末端ＯＨ比率が９５．０〜９９．５％であるポリカーボネートジオール（ｂ）とを反応させて両末端イソシアネート基のプレポリマーを得た後、水酸基含有ウレタン（メタ）アクリレート（ｃ）をさらに反応させる工程を含む、ウレタン（メタ）アクリレートの製造方法。

（但し、式中のＲは、炭素数２〜１２の二価の脂肪族又は脂環族炭化水素を表わす。）

［９］ ポリカーボネートジオール（ｂ）の分子量が９００〜１１００である、［８］に記載のウレタン（メタ）アクリレートの製造方法。
［１０］ ［１］から［５］のいずれか一つに記載のウレタン（メタ）アクリレートを含む、コーティング材料。
［１１］ ［１］から［５］のいずれか一つに記載のウレタン（メタ）アクリレートを含む、成型材料。
［１２］ ［６］または［７］に記載の配合組成物を含む、コーティング材料。
［１３］ ポリカーボネート樹脂、またはポリカーボネートとＡＢＳの複合体から成る樹脂に対するコーティング用途として使用される、［１０］または［１２］に記載のコーティング材料。
［１４］ ［６］または［７］に記載の配合組成物を含む、成型材料。
［１５］ ［１０］または［１２］に記載のコーティング材料を、ポリカーボネート樹脂、またはポリカーボネートとＡＢＳの複合体から成る樹脂にコーティングした、コーティング物。
［１６］ ［１５］に記載のコーティング物が、モバイル機器といわれる携帯電話、スマートフォン、携帯型音楽プレーヤー、パーソナルコンピューター躯体、およびそれらの保護カバー、保護フィルムのいずれかである、コーティング物。 That is, the present invention is as follows.
[1] An isocyanate compound (a) having at least two isocyanate groups, a polycarbonate diol (b) comprising a repeating unit represented by the following general formula (A) and a terminal hydroxyl group, a hydroxyl group-containing (meth) acrylate ( c) urethane (meth) acrylate which is a reaction product with the polycarbonate diol (b) as an essential repeating unit, a repeating unit represented by the following formula (B) and a repeating represented by the following formula (C) The total of the repeating unit represented by the following formula (B) and the repeating unit represented by the following formula (C) is 60 to 100 mol% of the entire repeating unit represented by the general formula (A). component:
Trimethylolpropane triacrylate 20 parts Urethane (meth) acrylate (as solids) 30 parts N-butyl acetate (total) 52 parts 1-hydroxycyclohexyl phenyl ketone A mixture containing 2 parts is coated on a polycarbonate plate and the film thickness is The coating film (film thickness: 20 μm) obtained by irradiating with an ultraviolet ray of 800 mJ / cm ² so as to be 20 μm is cured, and no peeling is observed in the cross-cut method (JIS-K-5600). A urethane (meth) acrylate having a color difference (ΔE) before and after removal of the applied oily black ink with isopropyl alcohol of 3 or less.

(However, R in the formula represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 12 carbon atoms.)

[2] The urethane (meth) acrylate according to [1], in which peeling is not recognized by the cross-cut method even after the coating film is immersed in warm water at 80 ° C. for 4 hours.
[3] The urethane (meth) acrylate according to [1] or [2], wherein the polycarbonate diol (b) has a primary terminal OH ratio of 95.0 to 99.5%.
[4] The urethane (meth) acrylate according to any one of [1] to [3], wherein the polycarbonate diol (b) has a molecular weight of 900 to 1100.
[5] The ratio of the direct adduct of the isocyanate compound (a) and the hydroxyl group-containing (meth) acrylate (c) generated during the reaction for obtaining the urethane (meth) acrylate is based on the total product obtained by the reaction. The urethane (meth) acrylate according to any one of [1] to [4], which is 0.1 to 12% by weight.
[6] A blended composition comprising the urethane (meth) acrylate according to any one of [1] to [5] and other (meth) acrylic acid esters.
[7] The composition according to [6], further including a polymerization initiator [8] An isocyanate compound (a) having at least two isocyanate groups and a repeating unit represented by the following general formula (A) And a repeating unit represented by the following formula (B) as an essential repeating unit, a repeating unit represented by the following formula (B), and a repeating unit represented by the following formula (B): A polycarbonate diol in which the total of the repeating units represented by (C) is 60 to 100 mol% of the entire repeating units represented by formula (A) and the primary terminal OH ratio is 95.0 to 99.5% After reacting with (b) to obtain a prepolymer of both end isocyanate groups, the hydroxyl group-containing urethane (meth) acrylate (c) is further reacted. Including extent, production method of the urethane (meth) acrylate.

(However, R in the formula represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 12 carbon atoms.)

[9] The method for producing a urethane (meth) acrylate according to [8], wherein the polycarbonate diol (b) has a molecular weight of 900 to 1100.
[10] A coating material comprising the urethane (meth) acrylate according to any one of [1] to [5].
[11] A molding material comprising the urethane (meth) acrylate according to any one of [1] to [5].
[12] A coating material comprising the composition according to [6] or [7].
[13] The coating material according to [10] or [12], which is used as a coating application for a polycarbonate resin or a resin composed of a composite of polycarbonate and ABS.
[14] A molding material comprising the composition according to [6] or [7].
[15] A coated product obtained by coating the coating material according to [10] or [12] on a polycarbonate resin or a resin composed of a composite of polycarbonate and ABS.
[16] A coating product according to [15], which is one of a mobile phone, a smartphone, a portable music player, a personal computer housing, and a protective cover and a protective film thereof, which are called mobile devices.

  The polycarbonate diol raw material urethane (meth) acrylate of the present invention is excellent in physical properties such as adhesion, stain resistance, chemical resistance, hydrolysis resistance, flexibility, and wear resistance, and satisfies all these physical properties. Therefore, by using it as a coating material or a molded product, durability that is an excellent practical physical property can be imparted, that is, the aesthetics can be maintained for a long time. Moreover, it does not require an excessive dilution solvent for viscosity adjustment, and has an effect of excellent appearance smoothness after curing. These characteristics are maximized in performance when used as a coating material for a polycarbonate resin or a mixed resin of a polycarbonate resin and another resin, and further as a coating material for mobile devices.

（但し、式中のＲは、炭素数２〜１２の二価の脂肪族又は脂環族炭化水素を表わす。）

Hereinafter, the urethane (meth) acrylate using the polycarbonate diol of the present invention as a raw material will be specifically described.
The urethane (meth) acrylate of the present invention is an isocyanate compound (a) having at least two or more isocyanate groups, a polycarbonate diol (b) comprising a repeating unit represented by the following general formula (A) and a terminal hydroxyl group, A urethane (meth) acrylate that is a reaction product with a hydroxyl group-containing (meth) acrylate (c), wherein the polycarbonate diol (b) is an essential repeating unit represented by the following formula (B) and the following formula: The total number of repeating units represented by the following formula (B) and the repeating units represented by the following formula (C) is 60 to This urethane (meth) acrylate is 100 mol%.

(However, R in the formula represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 12 carbon atoms.)

  In addition, the coating film obtained by curing the mixture containing urethane (meth) acrylate does not show peeling in the cross-cut method (JIS-K-5600), and the oil-based black ink applied to the coating film is isopropyl alcohol. The color difference (ΔE) before and after removal at the time of removal at 3 is 3 or less.

In order for the cured product to have durability, it is necessary to have excellent adhesion. For the evaluation of adhesion, a cross-cut method is used, and a mixture of the following component ratios containing the urethane (meth) acrylate of the present invention is applied on a polycarbonate plate and irradiated with ultraviolet rays of 800 mJ / cm ^2. It is necessary that no peeling is observed in the cured coating film (film thickness: 20 μm).
Trimethylolpropane triacrylate 20 parts Urethane (meth) acrylate of the present invention (as solid content) 30 parts n-butyl acetate (total) 52 parts 1-hydroxycyclohexyl phenyl ketone 2 parts

  A specific method is performed according to the JIS-K-5600 cross-cut method, and the result is also determined according to JIS. That is, if the six-step evaluation is “0”, the result is that the peeling described in the present specification is not recognized.

The stain resistance evaluated by the removability of the oil-based black ink is the removability of the commercially available oil-based marker (Magic Ink, registered trademark) by isopropyl alcohol (IPA) using the coating film prepared in the same manner as the evaluation of the adhesion. evaluate. First, paint with a bold type oil marker on the coating film so that the area is 1 cm ² or more, let stand for 1 minute, hang about 1 cc of IPA, lift the ink of the marker, and then wipe off all the ink gently with tissue paper The result is measured with a color difference meter. When the urethane (meth) acrylate of the present invention is used, the color difference ΔE is usually 3 or less. If ΔE is 3 or less, dirt in daily life and dirt due to intentional and unintentional contaminants can be suppressed to an inconspicuous degree. However, if ΔE is 2 or less, it is more difficult to visually judge. Is preferable.

(1) Isocyanate compound (a)
The isocyanate compound used in the present invention includes 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and mixtures thereof, crude tolylene diisocyanate (TDI), diphenylmethane-4,4′-diisocyanate (MDI), crude MDI, Fragrances such as naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI), polymethylene polyphenylene polyisocyanate (PMDI), dianidine diisocyanate, tetramethylxylylene diisocyanate Diisocyanates; aromatic aliphatic diisocyanates such as xylylene diisocyanate (XDI) and p-phenylene diisocyanate; 4,4′-methylenebiscyclohexyl diisocyanate (hydrogenated MDI) , Cycloaliphatic diisocyanates such as isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), norbornene diisocyanate (NBDI), hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2, Mention may be made of aliphatic diisocyanates such as 4,4-trimethylhexamethylene diisocyanate (TMDI) and mixtures thereof, dimer acid diisocyanate (DDI), lysine isocyanate. From the viewpoint of light resistance, weather resistance, etc., it is preferable to use alicyclic diisocyanate or aliphatic diisocyanate. Of these, isophorone diisocyanate having isocyanate groups with different reaction rates and easy molecular weight control is particularly preferred.
As the above isocyanate compounds, modified products such as carbodiimide modification, isocyanurate modification, biuret modification, allophanate modification, uretdione modification may be used, and blocked isocyanates blocked with various blocking agents may be used. In order not to cause gelation during the reaction, the isocyanate group is usually preferably bifunctional. Usually, one type of isocyanate is selected and used, but two or more types can be selected from these isocyanate compounds, and they can be mixed or sequentially added for use. Furthermore, a polyisocyanate having 3 or more isocyanate groups in one molecule can be used as long as it does not cause gelation during the reaction. Examples of polyisocyanates having 3 or more isocyanate groups in one molecule include the above-mentioned diisocyanate isocyanurate trimers, biuret trimers, trimethylolpropane adduct compounds, triphenylmethane triisocyanate, 1-methylbenzole-2, Examples include 4,6-triisocyanate and dimethyltriphenylmethane tetraisocyanate. Further, modified products such as isocyanurate modification and biuret modification may be used, and blocked isocyanates blocked with various blocking agents may be used.

（但し、式中のＲは、炭素数２〜１２の二価の脂肪族又は脂環族炭化水素を表わす。）

(2) Polycarbonate diol (b)
The polycarbonate diol (b) used in the present invention is a polycarbonate diol composed of a repeating unit represented by the following general formula (A) and a terminal hydroxyl group, and the repeating unit represented by the following formula (B) is an essential repeating unit. And polycarbonate diol (b). The repeating unit represented by the following formula (C) is preferably contained in the polycarbonate diol (b) because the viscosity and flexibility can be lowered by a combination with the following formula (B). The total of the repeating unit represented by the following formula (B) and the repeating unit represented by the following formula (C) is usually the repeating unit represented by the general formula (A) of the polycarbonate diol (b) (polycarbonate diol (b ) To 60 to 100 mol% of the entire repeating unit.

(However, R in the formula represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 12 carbon atoms.)

The primary terminal OH ratio of the polycarbonate diol (b) is usually 95.0 to 99.5%. The primary terminal OH ratio of the polycarbonate diol (b) is defined as the weight percentage of the diol having both primary terminals as primary hydroxyl groups with respect to the total alcohol excluding ethanol. The alcohol containing diol corresponds to the diol segment of the terminal portion of the polycarbonate diol, and the alcohol is heated at a temperature of 160 ° C. to 200 ° C. while stirring the polycarbonate diol under a pressure of 0.4 kPa or less. Is obtained as a fraction. Specifically, the primary terminal OH ratio in the present invention is such that 70 g to 100 g of the polycarbonate diol (b) is heated at a temperature of 160 ° C. to 200 ° C. with stirring under a pressure of 0.1 kPa or less. An amount of a fraction corresponding to about 1-2% by weight of the polycarbonate diol (b), ie, about 1 g (0.7-2 g) of an initial fraction, was obtained, and about 100 g (95-105 g) of ethanol was added. The value calculated by the following formula 1 from the value of the peak area of the chromatogram obtained by collecting the collected solution as a solvent and subjecting the collected solution to gas chromatography (GC) analysis.
Primary terminal OH ratio (%) = A ÷ B × 100 (1)
A: Sum of peak areas of diols whose both ends are primary OH groups B: Sum of peak areas of alcohols (excluding ethanol) containing diols)

  Specific examples of “alcohols containing diol (excluding ethanol)” detected in the GC analysis performed for the measurement of the primary terminal OH ratio are 1,5-pentanediol, 1,6- Examples include hexanediol, 1,4-butanediol, 1,5-hexanediol, 1,4-cyclohexanediol, 1,4-pentanediol, 1-butanol, 1-pentanol, and 1-hexanol. When the polycarbonate diol (b) is heated at a temperature of 160 ° C. to 200 ° C. with stirring under a pressure of 0.1 kPa or less as described above, one molecule of alcohol containing a terminal diol is formed by a condensation reaction between the polycarbonate diol polymers. A fraction obtained by the elimination reaction is obtained as a fraction, and the ratio of diols in which both ends are primary OH groups in all alcohols in this fraction is the primary terminal OH ratio.

  If the primary OH terminal ratio is in the above range, the reaction rate can be easily controlled, and various physical property balances such as high hydrolysis resistance, weather resistance, chemical resistance and flexibility can be expressed, and the viscosity can be adjusted. In this case, a polycarbonate diol raw material urethane (meth) acrylate excellent in surface smoothness after curing without requiring an excessive dilution solvent can be obtained. When the primary terminal OH group ratio exceeds 99.5%, the viscosity of the obtained polycarbonate diol raw material urethane (meth) acrylate becomes very high, and a large amount of dilution solvent is required to facilitate handling. In addition, the surface smoothness after curing also deteriorates.

  On the other hand, when a primary terminal OH group ratio of less than 95.0% is used as a raw material for the synthesis of urethane (meth) acrylate, the reaction rate with the reaction partner isocyanate becomes slow, and the rate control becomes difficult. In some cases, the obtained reactant may not exhibit the desired performance. For example, when isophorone diisocyanate, which is most preferable as the isocyanate used in the present invention, is used, the reaction rate of isophorone diisocyanate is relatively slower than that of other isocyanate species, which is unfavorably affected. Specifically, when there are many secondary terminal OH, the addition rate of the isocyanate to the polycarbonate diol terminal normally performed as the first reaction is slow, and it will interfere with industrial production. To advance this reaction quickly, there are methods of using a large amount of urethane reaction catalyst or raising the reaction temperature. However, both of these methods cause problems such as higher molecular weight due to side reactions and coloring. It is not preferable. When polycarbonate diol having many secondary terminal OH groups is used as a raw material under standard conditions so as not to cause these problems, a large amount of isocyanate (a) not added to polycarbonate diol (b) remains, and hydroxyl group-containing (meth) The acrylate (c) will be added directly. It is not preferable to increase the direct adduct composed of (a) and (c) which is not the product of the present invention, which can be said impurities, because the physical properties of the product of the present invention are deteriorated. On the other hand, when the reason why the primary OH group terminal is low is changed to something other than OH group, since isocyanate is not added, hydroxyl group-containing (meth) acrylate is not added to the terminal, and this lowers the final physical properties. It is not preferable.

  When the primary terminal OH group ratio is 95.0% to 99.5%, the above problem is less likely to occur. It is more preferable when the primary terminal OH group ratio is 97.0% to 99.0%.

For the production of the polycarbonate diol (b) of the present invention, 1,5-pentanediol is used as a raw material as an essential raw material. Preferably, 1,6-hexanediol is further used as a diol raw material. The purity of these diols is preferably 97.0% to 99.5%. More preferably, it is 98.0% or more to 99.0%.
In addition to 1,5-pentanediol and 1,6-hexanediol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,7-heptanediol, 1,8-octanediol, 1,9 -Diols having no side chain such as nanodiol, 1,10-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1,8-octanediol, 2-ethyl-1,6 -Hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentane Diol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, etc. Ol, 1,4-cyclohexanedimethanol, 2-bis (4-hydroxycyclohexyl) - cyclic diols such as propane, one or two or more diols can be used as a raw material. The amount is not particularly limited as long as the ratio of the repeating unit of the polycarbonate diol (b) specified in the present invention is satisfied.

  Further, a compound having 3 or more hydroxyl groups per molecule, for example, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, etc. may be used within the range not impairing the performance of the polycarbonate diol (b) of the present invention. it can. When too many compounds having three or more hydroxyl groups in one molecule are used, gelation occurs due to crosslinking during the polymerization reaction of the polycarbonate. Therefore, when a compound having 3 or more hydroxyl groups in one molecule is used, it is preferably 0.1 to 5% by weight based on the total amount of diols used as a raw material. More preferably, it is 0.1 to 2% by weight.

  As the carbonate of the polycarbonate diol (b) of the present invention, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate such as dibutyl carbonate, diaryl carbonate such as diphenyl carbonate, ethylene carbonate, trimethylene carbonate, 1,2- Examples include alkylene carbonates such as propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, and 1,2-pentylene carbonate. Among these, one or more carbonates can be used as a raw material. The use of dialkyl carbonate and / or diaryl carbonate is preferable because a polycarbonate diol satisfying a specific primary terminal OH ratio can be easily obtained by adjusting conditions such as the charging ratio of diol and carbonate. Moreover, it is more preferable to use ethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and dibutyl carbonate from the viewpoint of easy availability and ease of setting conditions for the polymerization reaction.

  In the production of the polycarbonate diol (b) of the present invention, a catalyst may or may not be added. When adding a catalyst, it can select freely from a normal transesterification catalyst. For example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium and other metals, salts, alkoxides, organic compounds Used. Particularly preferred are titanium, tin and lead compounds. Moreover, the usage-amount of a catalyst is 0.00001 to 0.1% of polycarbonate diol weight normally.

  The production of the polycarbonate diol (b) having a primary terminal OH ratio of the present invention is usually carried out in two stages. As a specific example, using a reactor equipped with a distillation apparatus, in the presence of a transesterification catalyst, a carbonate and a diol are subjected to a reaction temperature of 100 to 170 ° C. and a reduced pressure of 3.0 to 11.0 KPa. The first step of reacting while distilling off the alcohol derived from the carbonate and the carbonate to be azeotropically distilled, and the alcohol and the carbonate are distilled under a reduced pressure of 171 ° C. to 189 ° C. and 0.01 to 3.0 KPa. The manufacturing method etc. which include the 2nd process made to react while leaving are mentioned.

When the said manufacturing method of polycarbonate diol (b) is employ | adopted, the reaction temperature of a 1st process is 100-170 degreeC normally as above-mentioned, Preferably it is 120-165 degreeC, More preferably, it is 130-160 degreeC. If the reaction temperature in the first step is less than 100 ° C., the transesterification reaction becomes extremely slow and not only takes a long time for production, but also in the azeotropic fraction of alcohol and carbonate distilled during the first step. Further, the amount of carbonate is increased, and as a result, the yield of the resulting aliphatic polycarbonate diol is also decreased.
On the other hand, when the reaction temperature in the first step exceeds 170 ° C., for example, when ethylene carbonate is used as a raw material, a decomposition reaction easily occurs and the amount of ethylene oxide generated by the decomposition increases. Ethylene oxide reacts with an aliphatic dihydroxy compound or ethylene glycol produced by a reaction between ethylene carbonate and an aliphatic dihydroxy compound to produce a diol compound having an ether group. Since the diol compound having an ether group is finally taken into the main chain skeleton of the aliphatic polycarbonate diol, when the first step exceeds 170 ° C., the ether group content in the main chain skeleton of the aliphatic polycarbonate diol is reduced. It will increase. An increase in the ether group content is not preferable because the heat resistance and weather resistance of the aliphatic polycarbonate diol are lowered.

  In the first step, the reaction is usually carried out under a reduced pressure of 3.0 to 11.0 KPa, preferably 3.5 to 7.5 KPa, and the reaction is carried out while distilling off the carbonate-derived diol to be formed and the azeotropic carbonate. If the pressure is less than 3.0 KPa, the proportion of carbonate in the distillate increases, and the yield of the aliphatic polycarbonate diol finally obtained is not preferable. Moreover, when it exceeds 11.0 KPa, since the distillation rate of the carbonate-derived diol produced | generated at a 1st process and the carbonate azeotroped falls and reaction requires a long time, it is unpreferable.

  Next, the 2nd process of the manufacturing method of aliphatic polycarbonate diol in the said manufacturing method is demonstrated. The second step is a step of reacting diol and carbonate while distilling off under reduced pressure of 171 ° C. to 189 ° C. and 0.01 to 3.0 KPa.

  When the reaction temperature is less than 171 ° C., the time required to reach the desired degree of polymerization is undesirably increased. If the temperature exceeds 195 ° C., the terminal of the polycarbonate diol becomes a vinyl group due to side reactions, and the primary terminal OH ratio decreases, which is not preferable. The reaction temperature in the second step is more preferably 175 ° C. to 187 ° C., further preferably 180 ° C. to 185 ° C.

  In the said manufacturing method of polycarbonate diol (b), you may perform a 1st process and a 2nd process continuously in the same reaction container, and after performing a 1st process once, it is the same or different. The second step may be performed in the reaction vessel.

  Further, for the purpose of adjusting the primary terminal OH ratio within a predetermined range, a diol having a monoalcohol or a secondary alcohol is added during the production process or after completion of the polymerization in the second process and synthesized by a condensation reaction. You can also.

（但し、式中のＲは、炭素数２〜１２の二価の脂肪族又は脂環族炭化水素を表わす。）

In the polycarbonate diol (b) used in the present invention, the ratio of the total of repeating units represented by the following formulas (B) and (C) in the repeating unit represented by the following general formula (A) (hereinafter referred to as “principal component ratio”) Is usually 60 to 100 mol%. When the main component ratio is in the above range, urethane (meth) acrylate having a good performance balance such as hydrolysis resistance, heat resistance and flexibility can be obtained. If the main component ratio is 60 mol% or more, good flexibility can be obtained, and an increase in the viscosity of the polycarbonate diol (b) can be suppressed. When the main component ratio is 70 to 100 mol%, the above problem is less likely to occur, and when it is 85 to 100 mol%, it is more preferable.

(However, R in the formula represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 12 carbon atoms.)

In the polycarbonate diol (b) used in the present invention, the ratio of the repeating unit of the formula (B) to the repeating unit of the formula (C) (hereinafter referred to as “copolymerization ratio”, the above formula (B): the above formula (C In the case where the molar ratio is 25:75 to 75:25, the crystallinity of the polycarbonate diol (b) is lowered, and the handling during the production of the urethane (meth) acrylate is facilitated and obtained. Since the flexibility of urethane (meth) acrylate is also improved, it is preferable. Furthermore, it is more preferable when the copolymerization ratio is 35:65 to 65:35.
In order to make the copolymerization ratio of the polycarbonate diol (b) used in the present invention within the above range, in the production of the polycarbonate diol, 1,5-pentanediol having a lower boiling point tends to be distilled off more. Yes, it is necessary to increase the amount of 1,5-pentanediol. The molar ratio of 1,5-pentanediol and 1,6-hexanediol, which are raw material diols, is usually 28:72 to 83:17, preferably 39:61 to 72:28.
The range of the average molecular weight of the polycarbonate diol (b) used in the present invention is usually 300 to 3000 in terms of number average molecular weight. If the number average molecular weight is 300 or more, the flexibility of the urethane (meth) acrylate does not decrease, and if it is 3000 or less, the original viscosity is high to produce a raw material for the urethane (meth) acrylate. There is no difficulty in handling at the time and a situation of using a large amount of a diluted solvent. The number average molecular weight is more preferably in the range of 800 to 2000, and 900 to 1100 is most preferable because the balance of physical properties serving as an index of durability such as adhesion to the substrate and stain resistance can be achieved at a high level.

(3) Hydroxyl group-containing (meth) acrylate (c)
As the hydroxyl group-containing (meth) acrylate (c) used in the present invention, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, hydroxyhexyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-butylene glycol monoacrylate, glycerin monoacrylate, propylene glycol monoacrylate, polycaprolactone glycol monoacrylate, trimethylolpropane diacrylate, Pentaerythritol triacrylate, ditrimethylolpropane triacrylate, dipentaerythritol pen Acrylate and methacrylate, and the like to these acrylates can be used as raw materials as long as containing a hydroxyl group (meth) acrylate monomer. These can also be used independently and can also use 2 or more types together.

(4) Polycarbonate diol raw material urethane (meth) acrylate and synthesis thereof In the present invention, the polycarbonate diol raw material urethane (meth) acrylate includes a specific isocyanate compound (a), a polycarbonate diol (b), and a hydroxyl group-containing (meth) acrylate. It is a reaction product with (c). The polycarbonate diol raw material urethane (meth) acrylate can be obtained by a known method. For example, a method of reacting an isocyanate compound (a) with a polycarbonate diol (b) to synthesize a prepolymer having a terminal isocyanate group, and then reacting this with a hydroxyl group-containing (meth) acrylate (c), etc. There is.

In this invention, the compounding quantity of an isocyanate compound (a) is 1.5-5.0 normally by isocyanate group / hydroxyl group ratio with respect to the sum total of the hydroxyl group of polycarbonate diol (b), and 1.8-3.0 Is preferable. If the blending amount of the isocyanate compound (a) is 1.5 equivalents or less of the isocyanate group / hydroxyl group ratio, it will deviate from the object of the present invention because the molecular weight increases and the viscosity increases. If the isocyanate group / hydroxyl group ratio is within 5.0, unreacted organic isocyanate molecules can be reduced from the viewpoint of the reaction ratio, so that the amount other than the polycarbonate diol raw material urethane (meth) acrylate of the present invention is reduced to a small amount. Since it can suppress, it is preferable. An isocyanate group / hydroxyl group ratio of 1.9 to 2.1 is most preferred because the amount other than the objective can be further reduced. When reacted in this most preferred range, the direct adduct that can be said to be an impurity of the isocyanate compound (a) and the hydroxyl group-containing (meth) acrylate (c) is minimized, and the direct adduct with respect to the entire product obtained by the reaction. The ratio is from 0.1% to 12% or less.
In the present invention, the amount of the hydroxyl group-containing (meth) acrylate (c) is determined based on the hydroxyl group equivalent, and the isocyanate group of the terminal isocyanate group polymer obtained by the reaction of the isocyanate compound (a) and the polycarbonate diol (b). It is preferable that the equivalent and the hydroxyl equivalent are equal. If the amount is equal to or less than that, an isocyanate group remains at the terminal of the polymer, which is different from the present invention. In order to react all the isocyanate group terminals, it is possible to make the amount slightly larger than the equivalent amount in view of safety, but the preferred range is 1.0 to 1.5 in terms of the hydroxyl group / isocyanate group ratio. When the hydroxyl group / isocyanate group ratio is less than 1.0, the isocyanate group remains and adversely affects the storage stability. When the hydroxyl group / isocyanate group ratio exceeds 1.0, the component (c) is not taken into the structure of the present invention and exists as an acrylic monomer as it is, which impairs the degree of freedom in blending design. However, this is not the case when the component (c) that is not incorporated into the structure of the present invention is intentionally used as a blending constituent raw material for the coating composition or molding composition.

  The reaction between these isocyanate groups and hydroxyl groups, so-called urethane reaction, is usually carried out at 120 ° C. or lower. When the reaction temperature is high, it is difficult to control the reaction rate, so that the increase in the molecular weight proceeds more than necessary, which may cause thickening of the reaction product, formation of a gel-like product, coloring due to alteration, and the like. The reaction is usually carried out at 40 to 110 ° C, preferably 40 to 80 ° C. If the reaction temperature is too low, the reaction rate may become very slow, or the viscosity of the reaction product may become high and dispersion / mixing may be insufficient, making it difficult to obtain a uniform product.

  In this reaction, a urethane reaction catalyst can be added as necessary. Examples of the catalyst include tertiary amines such as triethylamine, metal salts such as potassium acetate, zinc stearate and tin octylate, and organometallic compounds such as dibutyltin dilaurate and dioctyltin dilaurate. The addition amount is usually 0.5 to 2000 ppm with respect to the reaction product.

In the reaction, an organic solvent can be used as necessary. Examples of the organic solvent include ester organic solvents such as butyl acetate and ethyl acetate, ketone organic solvents such as methyl ethyl ketone and acetone, and aromatic organic solvents such as toluene and xylene. These organic solvents can be used individually or in mixture of 2 or more types. When using an organic solvent, it is desirable not to use it more than necessary in order to cope with the environment by reducing VOC. A preferred range is usually 5 to 150% with respect to the total amount of the crosslinkable compound. Furthermore, a radical polymerization inhibitor can also be used. Examples of the radical polymerization inhibitor include hydroquinone monomethyl ether and phenothiazine.

(5) Coating composition and molding material The materials of the coating composition used in the present invention are described below.
The coating described in the present specification is to provide one or more cured product layers on the surface of an object, and the method is not particularly limited, but is performed by various general coating machines, printing machines, coaters and the like. Is called. As a classification of the coating material, various paints, inks, adhesive pressure-sensitive adhesives and the like can be mentioned.
The molded product is obtained by curing these materials into a certain shape, and the coating composition and the material to be used are basically the same.
In order to adjust the viscosity of the polycarbonate diol raw material urethane (meth) acrylate and to adjust the crosslinking density of the resin obtained by curing, an appropriate reactive diluent can be used. As reactive diluents, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, Dimethacrylates such as methylpentanediol diacrylate, tetraethylene glycol diacrylate, cyclohexanedimethanol diacrylate, polyethoxylate bisphenol A diacrylate, polyproxy hydrogenated bisphenol A diacrylate, and corresponding dimethacrylates; trimethylol Multifunctional acrylics such as propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate Esters and their corresponding polyfunctional methacrylic acid esters; tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, cyclohexyl acrylate, isobornyl acrylate, benzyl acrylate, phenyl acrylate, etc. and their corresponding meta Examples thereof include vinyl ester monomers such as acrylic ester, vinyl acetate, vinyl butyrate and divinyl adipate, and acrylamides such as acrylamide, N-vinylformaldehyde, N-vinyl-2-pyrrolidone and Nt-butylacrylamide. The addition amount of the diluent is not particularly limited as long as the properties of the polycarbonate diol raw material urethane (meth) acrylate of the present invention are not impaired, but when used, the polycarbonate diol raw material urethane (meth) acrylate of the present invention is used. It is preferable that it is 5 to 90% in the total weight. More preferably, it is 10-80. If it is 5% or more, the effect of dilution is obtained, and if it is 90% or less, the characteristics of the polycarbonate diol raw material urethane (meth) acrylate of the present invention are obtained. When using these reactive diluents, you may add at the time of the synthesis | combination for obtaining the polycarbonate diol raw material urethane (meth) acrylate of this invention, and you may add when setting it as a compounding composition.

  Since the polycarbonate diol raw material urethane (meth) acrylate of the present invention has a double bond of (meth) acryloyl group, it can be cured by heating if a thermal polymerization initiator is added, and a photopolymerization initiator is added. Then, it can be easily cured in a short time by ultraviolet irradiation using an ultraviolet fluorescent lamp or a high-pressure mercury lamp or electron beam irradiation. The concentration of these polymerization initiators is 0.1 to 20% by weight, preferably 1 to 10% by weight, more preferably 3 to 5% by weight, based on the total weight of the hydroxyl group-containing (meth) acrylate, polycarbonate diol and isocyanate compound. . When the polymerization initiator is less than 0.1% by weight, curing may be insufficient, and when it exceeds 20% by weight, the properties of the resulting cured product may be deteriorated.

  Examples of the thermal polymerization initiator include peroxides such as benzoyl peroxide, lauroyl peroxide, bis- (4-t-butylcyclohexyl) peroxydicarbonate, and 2,2′-azobis-isobutyronitrile, Examples include azo compounds such as 2,2′-azobis-2,4-dimethylvaleronitrile. These thermal polymerization initiators can be used alone or in combination of two or more. The heating temperature varies depending on the adhesion and the substrate to be applied, but is usually from room temperature to 90 ° C, preferably from 40 ° C to 80 ° C.

  Examples of the photopolymerization initiator include benzophenone, ω-bromoacetophenone, chloroacetone, acetophenone, diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, p, p'-dichlorobenzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl ether, benzoin-n -Butyl ether, benzyl methyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, methylbenzoy Formate, 2,2-diethoxyacetophenone, 4-N, carbonyl-based photopolymerization initiators such as N'- dimethyl acetophenone. Furthermore, sulfide photopolymerization initiators such as diphenyl disulfide, dibenzyl disulfide and tetraethylmethylammonium sulfide, quinone photopolymerization initiators such as benzoquinone, t-butylanthraquinone and 2-ethylanthraquinone, 2,2′-azobispropane , Azo photopolymerization initiators such as hydrazine, thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, peroxide photopolymerization initiators such as benzoyl peroxide and di-t-butyl peroxide Agents and the like. These photopolymerization initiators can be used alone or in combination of two or more.

  Further, if necessary, a photopolymerization initiator and a known photosensitizer can be used in combination. Examples of the photosensitizer include 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone and the like. I can decide.

  For the purpose of improving storage stability, antioxidants and light stabilizers such as hindered amines, hindered phenols, and benzotriazoles can be used. Examples of these include ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB PEP-4C ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 329A, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB Made by Co., Ltd.), Sumizer BHT, Summarizer S, Summarizer BP-76, Summarizer MDP-S, Summarizer GM, Summarizer BBM-S, Millizer WX-R, Summarizer NW, Summarizer BP-101, Summarizer GA-80, Summarizer TNP, Summarizer BP-179, Sumilizer TPP-R, Summarizer P-16 (above, manufactured by Sumitomo Chemical Co., Ltd.), Tinuvin 770, Tinuvin 765 Tinuvin 144, Tinuvin 622, Tinuvin 111, Tinuvin 123, Tinuvin 292 (manufactured by BASF Japan Ltd.) and the like. Although the addition amount of these antioxidants and light stabilizers is not particularly limited, when used, it is usually used in an amount of 0.001 to 5% by weight based on the blend composition containing the polycarbonate diol raw material urethane (meth) acrylate.

In addition, various substances such as natural or synthetic polymer substances, fillers, pigments, leveling agents, modifiers, plasticizers, thixotropic agents, thickeners, and extenders may be added as necessary. Absent. These compounding amounts can be appropriately determined according to the application within a range not impairing the performance of the present invention.
(6) Coated products, molded products The products of the present invention are specifically used for coating information appliances such as mobile phones, smartphones and personal computers, coating optical films and films for building materials, special lenses, etc. Examples include UV curable molded articles, automobile interior parts, and exterior parts. Among them, the surfaces of parts such as mobile phones, smartphones, portable music players, personal computer enclosures, and their protective covers and protective films, which are so-called mobile devices that are touched by people and carried in bags etc. It is preferable to be used for coating purposes because the effects of the present invention can be exhibited most. The material of these objects to be coated is not particularly limited among plastic, wood, paper, and metal. However, when coated with a polycarbonate diol resin or a resin composed of a composite of ABS and polycarbonate diol, the best performance can be obtained.

Next, although an example and a comparative example explain the present invention, these examples do not limit the present invention at all.
The values shown in the following examples and comparative examples were measured by the following methods.

1) Primary terminal OH ratio The primary terminal OH ratio of the polycarbonate diol was measured by the following method. Weigh 70g to 100g of polycarbonate diol in a 300cc eggplant flask and heat at about 180 ° C under stirring under a pressure of 0.1 kPa or less using a rotary evaporator connected to a trap bulb for collecting fractions. The polycarbonate diol is heated in a bath to obtain a fraction equivalent to 1 to 2% by weight of the polycarbonate diol in the trap sphere, i.e. about 1 g (0.7 to 2 g) of the initial fraction. 100 g (95 to 105 g) of ethanol was recovered as a solvent, and the recovered solution was calculated from the peak area value of the chromatogram obtained by GC analysis according to the following formula (1).

Primary terminal OH ratio (%) = A ÷ B × 100 (1)
A: Sum of peak areas of diols having both primary OH groups at both ends B: Sum of peak areas of alcohols (excluding ethanol) containing diol Gas chromatographic analysis conditions: Column; DB-WAX (US & J Company) Manufactured), 30 m, film thickness 0.25 μm, temperature rising condition: 60 ° C. to 250 ° C., detector: FID (flame ionization detector).

2) Number average molecular weight of polycarbonate diol (b) Hydroxyl value was determined by “neutralization titration method (JIS K 0070-1992)” using acetic anhydride and pyridine and titrating with an ethanol solution of potassium hydroxide. 2).
Number average molecular weight = 2 / (OH value × 10 ⁻³ /56.1) (2)

3) Copolymerization ratio and main component ratio of polycarbonate diol (b) 1 g of a sample of polycarbonate diol (b) was taken into a 100 ml eggplant flask, and 30 g of ethanol and 4 g of potassium hydroxide were added and reacted at 100 ° C. for 1 hour. After cooling the reaction solution to room temperature, 2-3 drops of phenolphthalein was added to the indicator and neutralized with hydrochloric acid. After cooling in the refrigerator for 1 hour, the precipitated salt was removed by filtration and analyzed using GC (gas chromatography). GC analysis was performed using gas chromatography GC-14B (manufactured by Shimadzu Corporation, Japan) with DB-WAX (manufactured by J & W, USA) as a column, diethylene glycol diethyl ester as an internal standard, and a detector as FID. The temperature rising profile of the column was maintained at 60 ° C. for 5 minutes and then heated to 250 ° C. at 10 ° C./min.
(I) Copolymerization ratio Using the above analysis results, the copolymerization ratio (total number of moles of 1,5-pentanediol: 1,6- The total number of moles of hexanediol) was determined.
(Ii) Main component ratio The main component ratio was determined by the following mathematical formula (3) based on the above analysis results.
Main component ratio (mol%) = (B + C) / A × 100 (3)
A: Total number of moles of diol derived from the repeating unit of the above general formula (A)
B: Total number of moles of 1,5-pentanediol
C: Total number of moles of 1,6-hexanediol

4) Purity analysis of raw material diol 1,4-butanediol, 1,5-hexanediol and 1,6-hexanediol used as diol raw materials were analyzed by gas chromatography. The conditions were gas chromatography GC-14B (manufactured by Shimadzu Corporation) with DB-WAX (manufactured by J & W) as a column, diethylene glycol diethyl ester as an internal standard, and a detector as FID. The temperature rising profile of the column was maintained at 60 ° C. for 5 minutes and then heated to 250 ° C. at 10 ° C./min.

5) Isocyanate group amount The isocyanate group amount of the isocyanate compound (a) was determined by back titration with 1N hydrochloric acid after neutralizing the isocyanate group with an excess of 2N amine.

6) Urethane (meth) acrylate viscosity The viscosity of the obtained urethane (meth) acrylate was measured at 25 ° C using an E-type viscometer manufactured by Tokimec Corporation.

7) Isocyanate direct adduct content The content of the direct adduct of the isocyanate compound (a) and the hydroxyl group-containing (meth) acrylate (c) contained in the reaction product was analyzed by GPC (manufactured by Tosoh Corporation).

Polymerization example 1 of polycarbonate diol (b)
1,5-pentanediol and 1,6-hexanediol used as raw materials were analyzed. The 1,5-pentanediol had a purity of 98.4%, 1.1% by weight of 1,5-hexanediol, and 0.1% by weight of 1,4-cyclohexanediol. The remaining 0.4% by weight was a plurality of unknowns. 1,6-hexanediol had a purity of 98.9% and contained 0.6% by weight of 1,4-cyclohexanediol. The remaining 0.5% by weight was a plurality of unknowns. Except for Polymerization Example 6 and Comparative Examples 3 and 4 of polycarbonate diol (b), the polymerization examples and Comparative Examples used the raw materials.

In a 2 L glass flask equipped with a rectifying column packed with a regular packing and a stirring device, 485 g (5.4 mol) of dimethyl carbonate, 310 g (3.0 mol) of 1,5-pentanediol, 1,6- 300 g (2.5 mol) of hexanediol was charged. Add 0.08g of titanium tetrabutoxide as a catalyst, heat and stir at a temperature of 140-150 ° C under a pressure of 4.0-5.0kPa, react for 10 hours while distilling off the resulting mixture of methanol and dimethyl carbonate. did. Thereafter, the reaction was carried out at a reaction temperature of 180 ° C. to 185 ° C. and a pressure of 1.0 to 3.0 kPa for 3 hours while distilling off the resulting mixture of methanol and dimethyl carbonate. Then, it reacted at 185 degreeC for 5 hours, reducing pressure gradually to 0.5kPa.
The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC-1.

Polymerization example 2 of polycarbonate diol (b)
Using the same apparatus as the polymerization example 1 for polycarbonate diol, 380 g (4.2 mol) of dimethyl carbonate, 320 g (3.1 mol) of 1,5-pentanediol, and 140 g (1.2 mol) of 1,6-hexanediol were charged. It is. As a catalyst, 0.05 g of titanium tetrabutoxide was added, and the reaction was performed under the same conditions as in Synthesis Example 1 for polycarbonate diol. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC-2.

Polycarbonate diol polymerization example 3
Using the same apparatus as in Polymerization Example 1 for polycarbonate diol, 590 g (5.0 mol) of diethyl carbonate, 280 g (2.7 mol) of 1,5-pentanediol, and 300 g (2.5 mol) of 1,6-hexanediol were charged. It is. Titanium tetrabutoxide 0.09 g was added as a catalyst, and the reaction was performed under the same conditions as in Synthesis Example 1 for polycarbonate diol. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC-3.

Polycarbonate diol polymerization example 4
Using the same apparatus as in Polymerization Example 1 for polycarbonate diol, 590 g (5.0 mol) of diethyl carbonate, 200 g (1.9 mol) of 1,5-pentanediol, 280 g (2.4 mol) of 1,6-hexanediol, 80 g (0.9 mol) of 1,4-butanediol was charged. Add 0.09g of titanium tetrabutoxide as a catalyst, heat and stir at a temperature of 140-150 ° C under a pressure of 4.0-5.0 kPa, and react for 10 hours while distilling off the resulting ethanol and diethyl carbonate mixture. did. Thereafter, the reaction was carried out at a reaction temperature of 175 ° C. to 185 ° C. and a pressure of 1.0 to 3.0 kPa for 5 hours while distilling off the resulting mixture of ethanol and diethyl carbonate. Then, it reacted at 185 degreeC for 8 hours, reducing pressure gradually to 0.5kPa. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC-4.
When 1,4-butanediol used as a raw material was analyzed, the purity was 99.6% by weight, and 0.4% by weight was a plurality of unknown substances.

Polycarbonate diol polymerization example 5
Using the same apparatus as in Polymerization Example 1 for polycarbonate diol, 450 g (5.1 mol) of ethylene carbonate, 260 g (2.5 mol) of 1,5-pentanediol, and 310 g (2.6 mol) of 1,6-hexanediol were charged. It is. 0.10 g of titanium tetrabutoxide was added as a catalyst, and the mixture was stirred and heated at normal pressure. The reaction was carried out at a reaction temperature of 140 ° C. to 150 ° C. and a pressure of 4.0 to 5.0 kPa for 10 hours while distilling off the mixture of ethylene glycol and ethylene carbonate to be produced. Thereafter, the pressure was reduced to 0.5 kPa, and the reaction was further performed at 180 ° C. for 5 hours while distilling off ethylene carbonate and diol. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC-5.

Polycarbonate diol polymerization example 6
1,5-pentanediol and 1,6-hexanediol used in Polymerization Examples 1 to 5 were purified by distillation. As a result, with respect to 1,5-pentanediol, the purity was 98.9%, 1,5-hexanediol was 0.3% by weight, and 1,4-cyclohexanediol was not detected. The remaining 0.8% by weight was a plurality of unknowns. The 1,6-hexanediol had a purity of 99.2% and contained 0.2% by weight of 1,4-cyclohexanediol. The remaining 0.6% by weight was a plurality of unknowns. Polycarbonate diol was polymerized using the above raw materials.
Polymerization of polycarbonate diol except that 590 g (5.0 mol) of diethyl carbonate, 280 g (2.7 mol) of purified 1,5-pentanediol, and 300 g (2.5 mol) of purified 1,6-hexanediol were used. The reaction was carried out using the apparatus and conditions shown in Example 1. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC-6.

Comparative Example 1 of polycarbonate diol
Using the same apparatus as in Polymerization Example 1 for polycarbonate diol, 590 g (5.0 mol) of diethyl carbonate, 280 g (2.7 mol) of 1,5-pentanediol, and 300 g (2.5 mol) of 1,6-hexanediol were charged. It is. Add 0.09g of titanium tetrabutoxide as a catalyst, heat and stir at a temperature of 140-150 ° C under a pressure of 4.0-5.0 kPa, and react for 10 hours while distilling off the resulting ethanol and diethyl carbonate mixture. did. Thereafter, the reaction was carried out at a reaction temperature of 180 ° C. to 210 ° C. and a pressure of 4.0 to 6.0 kPa for 3 hours while distilling off the resulting mixture of ethanol and diethyl carbonate. Then, it reacted at 210 degreeC for 3 hours, reducing pressure gradually to 0.5kPa. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC-7.

Comparative example 2 of polycarbonate diol
Using the same apparatus as in Polymerization Example 1 for polycarbonate diol, 440 g (4.9 mol) of dimethyl carbonate and 590 g (5.0 mol) of 1,6-hexanediol were charged. Titanium tetrabutoxide 0.09 g was added as a catalyst, and the reaction was performed under the same conditions as in Synthesis Example 1 for polycarbonate diol. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC-8.

Comparative Example 3 of polycarbonate diol
Polymerization was performed using the same apparatus as in polymerization example 1 of polycarbonate diol, using the purified 1,5-pentanediol and 1,6-hexanediol used in polymerization example 6. For ethylene carbonate 450g (5.1mol), purity 98.9% 1,5-pentanediol 260g (2.5mol), purity 99.2% 1,6-hexanediol 310g (2.6mol) The reaction was performed under the conditions shown in Polymerization Example 5 for polycarbonate diol, except for the above. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC-9.

Comparative Example 4 of polycarbonate diol
1,5-pentanediol and 1,6-hexanediol different from the raw materials used in Polymerization Examples 1 to 6 were prepared and analyzed. The prepared 1,5-pentanediol had a purity of 96.2%, 2.5% by weight of 1,5-hexanediol, and 0.5% by weight of 1,4-cyclohexanediol. The remaining 0.8% by weight was a plurality of unknowns. The prepared 1,6-hexanediol had a purity of 96.7% and contained 0.8% by weight of 1,4-cyclohexanediol. The remaining 2.5% by weight was a plurality of unknowns. The prepared 1,5-pentanediol and 1,6-hexanediol were used for polymerization using the same apparatus as in Polymerization Example 1 for polycarbonate diol. 380 g (4.2 mol) of dimethyl carbonate, 320 g (3.1 mol) of 1,5-pentanediol, and 140 g (1.2 mol) of 1,6-hexanediol were charged. 0.05 g of titanium tetrabutoxide was added as a catalyst, and the reaction was performed under the conditions shown in Polymerization Example 1. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC-10.
Urethane (meth) acrylate was produced using the above polycarbonate diol.

Polycarbonate diol polymerization example 7
To the polycarbonate diol obtained in Comparative Example 3, 6.5 g (0.05 mol) of monoalcohol (2-ethylhexanol) was added. After heating to 150 ° C., the pressure was reduced to 0.5 kPa and the reaction was allowed to proceed for 2 hours while distilling off the diol. The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC-11.

Polycarbonate diol polymerization example 8
Using the same apparatus as the polymerization example 1 for polycarbonate diol, 485 g (5.4 mol) of dimethyl carbonate, 310 g (3.0 mol) of 1,5-pentanediol, and 300 g (2.5 mol) of 1,6-hexanediol were charged. It is. Add 0.08g of titanium tetrabutoxide as a catalyst, heat and stir at a temperature of 140-150 ° C under a pressure of 4.0-5.0kPa, react for 10 hours while distilling off the resulting mixture of methanol and dimethyl carbonate. did. Thereafter, the reaction was carried out at a reaction temperature of 180 ° C. to 185 ° C. and a pressure of 1.0 to 3.0 kPa for 2 hours while distilling off the resulting mixture of methanol and dimethyl carbonate. Then, it reacted at 185 degreeC for 3 hours, reducing pressure gradually to 0.5kPa.
The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC-12.

Polycarbonate diol polymerization example 9
Using the same apparatus as the polymerization example 1 for polycarbonate diol, 485 g (5.4 mol) of dimethyl carbonate, 310 g (3.0 mol) of 1,5-pentanediol, and 300 g (2.5 mol) of 1,6-hexanediol were charged. It is. Add 0.08g of titanium tetrabutoxide as a catalyst, heat and stir at a temperature of 140-150 ° C under a pressure of 4.0-5.0kPa, react for 10 hours while distilling off the resulting mixture of methanol and dimethyl carbonate. did. Thereafter, the reaction was carried out at a reaction temperature of 180 ° C. to 185 ° C. and a pressure of 1.0 to 3.0 kPa for 4 hours while distilling off the resulting mixture of methanol and dimethyl carbonate. Then, it reacted at 185 degreeC for 7 hours, reducing pressure gradually to 0.5kPa.
The results of analyzing the obtained polycarbonate diol are shown in Table 1. This polycarbonate diol is referred to as PC-13.

Urethane acrylate synthesis example 1
Isophorone diisocyanate (43.6 g) was placed in a 500 ml four-necked flask equipped with a stirrer, a condenser tube, a nitrogen inlet tube, and a thermometer. Nitrogen was introduced into the flask at an amount of 0.1 cc / min, heated to 50 ° C. using an oil bath while stirring, 0.01 g of dibutyltin dilaurate was added as a catalyst, and 100 g of polycarbonate diol PC was added using a dropping funnel. -1 and a mixed solution of 72.0 g of n-butyl acetate was added dropwise over 1 hour. Since the reaction end point of this mixed solution is confirmed by confirming that the reaction has reached equilibrium and has reached the calculated amount of residual isocyanate groups, the PC-1 dropping is completed 2 hours 30 minutes and 3 hours later. The residual amount of isocyanate was measured by titration. As a result of the measurement, it was confirmed that the residual amount was close to the theoretical value and the reaction reached equilibrium. After heating the reaction solution to 70 ° C., 0.02 g of dibutyltin dilaurate was added, the nitrogen inflow was stopped, and a solution in which 25.5 g of 2-hydroxyethyl methacrylate and 0.02 g of hydroquinone monomethyl ether were uniformly mixed was obtained. Using another dropping funnel, the mixture was added dropwise over 1 hour, and the mixture was further stirred for 3 hours to be reacted. It was confirmed by titrating the amount of residual isocyanate that the reaction rate of isocyanate was 99% or more. The obtained urethane acrylate is referred to as UAP-1, and the viscosity measurement results and the direct adduct content measurement results in the reaction product are shown in Table 2.

Urethane acrylate synthesis example 2
Using the same apparatus as in Synthesis Example 1, except that the polycarbonate diol was changed to PC-2, isophorone diisocyanate was 47.9 g, n-butyl acetate was 75.4 g, and 2-hydroxyethyl methacrylate was 28.1 g. Other raw materials and reaction conditions were operated in the same manner as in Synthesis Example 1 to obtain urethane acrylate. The urethane acrylate is referred to as UAP-2, and the viscosity measurement results and the direct adduct content measurement results in the reaction product are shown in Table 2.

Urethane acrylate synthesis example 3
Example of synthesis of equipment, other raw materials and reaction conditions except that polycarbonate diol is replaced with PC-3, isophorone diisocyanate is 41.1 g, n-butyl acetate is 71.0 g, and 2-hydroxyethyl methacrylate is 24.0 g. In the same manner as in No. 1, urethane acrylate was obtained. The urethane acrylate is referred to as UAP-3, and the viscosity measurement results and the direct adduct content measurement results in the reaction product are shown in Table 2.

Urethane acrylate synthesis example 4
Synthesis example of equipment, other raw materials and reaction conditions except that polycarbonate diol is replaced with PC-4, isophorone diisocyanate is 42.8 g, n-butyl acetate is 72.0 g and 2-hydroxyethyl methacrylate is 25.1 g. In the same manner as in No. 1, urethane acrylate was obtained. The urethane acrylate is referred to as UAP-4, and the viscosity measurement results and the direct adduct content measurement results in the reaction product are shown in Table 2.

Urethane acrylate synthesis example 5
Synthesis example of equipment, other raw materials and reaction conditions except that polycarbonate diol is replaced with PC-5, isophorone diisocyanate is 42.5 g, n-butyl acetate is 72.0 g and 2-hydroxyethyl methacrylate is 24.9 g. In the same manner as in No. 1, urethane acrylate was obtained. The urethane acrylate is referred to as UAP-5, and the viscosity measurement results and the direct adduct content measurement results in the reaction product are shown in Table 2.

Urethane acrylate synthesis example 6
Synthesis example of equipment, other raw materials and reaction conditions except that polycarbonate diol is replaced with PC-6, isophorone diisocyanate is 45.3 g, n-butyl acetate is 74.0 g and 2-hydroxyethyl methacrylate is 26.5 g. In the same manner as in No. 1, urethane acrylate was obtained. The urethane acrylate is referred to as UAP-6, and the viscosity measurement results and the direct adduct content measurement results in the reaction product are shown in Table 2.

Urethane acrylate synthesis example 7
Example of synthesis of equipment, other raw materials and reaction conditions except that polycarbonate diol is replaced with PC-11, isophorone diisocyanate is 42.3 g, n-butyl acetate is 72.0 g, and 2-hydroxyethyl methacrylate is 24.8 g. In the same manner as in No. 1, urethane acrylate was obtained. The urethane acrylate is referred to as UAP-7, and the viscosity measurement results and the direct adduct content measurement results in the reaction product are shown in Table 2.

Urethane acrylate synthesis example 8
Synthesis Example 1 except for using 32.9 g of hexamethylene diisocyanate instead of isophorone diisocyanate, 68.0 g of n-butyl acetate, and 24.7 g of 2-hydroxyethyl methacrylate as diisocyanate. In the same manner as above, urethane acrylate was obtained. The urethane acrylate is referred to as UAP-8, and the viscosity measurement results and the direct adduct content measurement results in the reaction product are shown in Table 2.

Urethane acrylate synthesis example 9
Except for using 83.6 g of pentaerythritol triacrylate (70 wt% triacrylate) as the hydroxyl group-containing acrylate, 43.6 g of isophorone diisocyanate, and 97.0 g of n-butyl acetate, the equipment, other raw materials, and reaction conditions By operating in the same manner as in Synthesis Example 1, urethane acrylate was obtained. The urethane acrylate is referred to as UAP-9, and the viscosity measurement results of the obtained urethane acrylate and the direct adduct content measurement results in the reaction product are shown in Table 2.

Urethane acrylate synthesis example 10
Synthesis example of equipment, other raw materials and reaction conditions except that polycarbonate diol is replaced with PC-12, isophorone diisocyanate is 56.0 g, n-butyl acetate is 80.9 g, and 2-hydroxyethyl methacrylate is 32.8 g. In the same manner as in No. 1, urethane acrylate was obtained. The urethane acrylate is referred to as UAP-10, and the viscosity measurement results and the direct adduct content measurement results in the reaction product are shown in Table 2.

Urethane acrylate synthesis example 11
Synthesis example of equipment, other raw materials, and reaction conditions except that polycarbonate diol is replaced with PC-13, isophorone diisocyanate is 22.1 g, n-butyl acetate is 57.9 g, and 2-hydroxyethyl methacrylate is 12.9 g. In the same manner as in No. 1, urethane acrylate was obtained. The urethane acrylate is referred to as UAP-11, and the viscosity measurement result of the direct adduct content measurement result in the reaction product is shown in Table 2.

Urethane acrylate synthesis comparative example 1
Synthesis Example 1 except for replacing polycarbonate diol with PC-7, isophorone diisocyanate 38.8 g, n-butyl acetate 69.5 g, 2-hydroxyethyl methacrylate 23.4 g In the same manner as above, urethane acrylate was obtained. The urethane acrylate is referred to as UAP-12, and the viscosity measurement results and the direct adduct content measurement results in the reaction product are shown in Table 2.

Urethane acrylate synthesis comparative example 2
The polycarbonate diol was replaced with PC-8, isophorone diisocyanate was 46.3 g, n-butyl acetate was 74.0 g, 2-hydroxyethyl methacrylate was 27.1 g, and solid PC-8 was heated to 50 ° C. Except for the operation of returning to a liquid state, the apparatus, other raw materials, and reaction conditions were operated in the same manner as in Synthesis Example 1 to obtain urethane acrylate. The urethane acrylate is referred to as UAP-13, and the viscosity measurement results and the direct adduct content measurement results in the reaction product are shown in Table 2.

Urethane acrylate synthesis comparative example 3
Using the same apparatus as in Synthesis Example 1, the reaction was carried out by replacing polycarbonate diol with PC-9. 44.3 g of isophorone diisocyanate was placed in a four-necked flask. After heating to 50 ° C. with stirring, 0.01 g of dibutyltin dilaurate was added as a catalyst, and a mixed solution of 100 g of polycarbonate diol PC-9 and n-butyl acetate was added dropwise over 1 hour using a dropping funnel. . Since the reaction end point of this mixed solution is confirmed by confirming that the reaction has reached an equilibrium as in Synthesis Example 1 and has reached the vicinity of the calculated residual amount of isocyanate groups, 1 hour 30 minutes after the completion of dropping of PC-9 and The amount of residual isocyanate after 2 hours was measured by titration. As a result of the measurement, since it was confirmed that the viscosity increased and stirring became difficult at that time, 97.7 g of n-butyl acetate was added to the flask. Since it was confirmed that the viscosity of the reaction solution decreased and stirring became easy by addition, nitrogen was introduced into the flask at an amount of 0.1 cc / min, and the reaction solution was heated to 70 ° C., and then dibutyltin dilaurate was added. Add 0.02 g, stop the nitrogen inflow, add a solution in which 25.9 g of 2-hydroxyethyl methacrylate and 0.02 g of hydroquinone monomethyl ether are uniformly mixed, using another dropping funnel over 1 hour, The reaction was stirred for 3 hours. It was confirmed by titrating the amount of residual isocyanate that the reaction rate of isocyanate was 99% or more. The obtained urethane acrylate is referred to as UAP-14, and the viscosity measurement results and the direct adduct content measurement results in the reaction product are shown in Table 2.

Urethane acrylate synthesis comparative example 4
Using the same apparatus as in Synthesis Example 1, synthesis was performed by replacing polycarbonate diol with PC-10. 48.8 g of isophorone diisocyanate was added, nitrogen was introduced at a rate of 0.1 cc / min, heated to 50 ° C. with stirring, 0.01 g of dibutyltin dilaurate was added as a catalyst, and 100 g of polycarbonate was added using a dropping funnel. A mixed solution of Diol PC-10 and 76.0 g of n-butyl acetate was added dropwise over 1 hour, and the reaction was further stirred for 3 hours. When the residual amount of isocyanate groups was confirmed by titration at that time, it was confirmed that the reaction was far from the theoretical value and the reaction did not proceed to the end. Therefore, the temperature was raised to 70 ° C. and the reaction was continued with stirring for 2 hours. I let you. Since there was no change in the analysis result of the residual isocyanate group at that time and the reaction result at the time of reaction at the same temperature for 30 minutes, 0.02 g of dibutyltin dilaurate was added, and then the nitrogen inflow was stopped. Then, a solution in which 28.6 g of 2-hydroxyethyl methacrylate and 0.02 g of hydroquinone monomethyl ether were uniformly mixed was added dropwise using another dropping funnel over 1 hour, and further stirred for 3 hours to be reacted. . It was confirmed by titrating the amount of residual isocyanate that the reaction rate of isocyanate was 99% or more. The obtained urethane acrylate is referred to as UAP-15, and the viscosity measurement results and the direct adduct content measurement results in the reaction product are shown in Table 2.

Example of paint formulation As a compounding composition, synthesized urethane acrylate (UAP-1 to UAP-15), trimethylpropane triacrylate (TMPTA) as other acrylate component, and Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) as a photopolymerization initiator ) Were used (Table 3). For the purpose of improving the coating surface finish of the blended composition, n-butyl acetate was used as a diluent for adjusting the viscosity. Compounding Comparative Example 2 was compounded after heating at 50 ° C. for 4 hours because the synthesized UAP-11 was crystallized and immediately used for coating. In addition, the blending in Table 3 is adjusted so that the solid content is 70%. However, in the blending comparative example 3, since the synthesized UAP-3-derived n-butyl acetate is contained in a large amount, the solid content is not added. Was less than 70%, and was used for evaluation without using additional n-butyl acetate. In addition, the adhesiveness, secondary adhesiveness, and stain resistance test described below were prepared by blending the components at the following ratios to prepare cured coating films (examples of these blended compositions are test blending examples, tests) This will be referred to as a comparative blending example).
20 g of trimethylolpropane triacrylate
Urethane (meth) acrylate (solid content) 30g
N-Butyl acetate (total) 52g
Photoinitiator (Irgacure 184) 2g
―――――――――――――――――――――――――――――
104g

Coating Film Evaluation Example 1) Adhesiveness Adhesiveness, which is one of durability indexes, was evaluated. 20 parts of trimethylolpropane triacrylate, 30 parts of urethane (meth) acrylate (solid content), 52 parts of n-butyl acetate, and 2 parts of photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) The compounded composition was applied onto a polycarbonate plate having a thickness of about 2 mm, a width of 100 mm, and a length of 150 mm with an applicator so that the film thickness after curing was about 20 μm, and a UV irradiation machine (Oak Manufacturing Co., Ltd., Handy UV). -300) was UV photopolymerized at an illuminance of 800 mJ / cm ² to obtain a cured coating film. About the obtained cured coating film, adhesiveness with a base material was evaluated using the JIS-K-5600 crosscut method (23 degreeC). Visually observed in 6 stages, with 0 indicating no peeling or chipping of the crosscut portion, 1 indicating that the crosscut portion is chipped and slightly peeled, and 5 indicating that the crosscut surface has peeled 35% or more. Was judged. The evaluation results are shown in Table 4.

2) Secondary adhesion In the positioning of the durability promotion test, the secondary adhesion was evaluated so that the influence of heat and hydrolysis could be confirmed. A cured coating film is prepared in the same manner as in 1) above, and the cured coating film is immersed as it is (without peeling or crosscutting) at 80 ° C. for 4 hours, and then cooled to room temperature, followed by JIS-K-5600 crosscut method. It was evaluated with. The evaluation criteria are the same as in 1). The evaluation results are shown in Table 4.

3) Contamination resistance test The following test is conducted as a method for evaluating the resistance to dirt by human hands, environmental dirt, and dirt (for example, coffee and hair dyes) encountered in places where people intentionally and unintentionally adhere. went. A white carbonate plate was used as a substrate, and a cured coating film was prepared in the same manner as in 1) above, and used for evaluation of stain resistance. As an evaluation of stain resistance, the removability of a commercially available oily marker (magic ink, registered trademark) with isopropyl alcohol (IPA) was confirmed. First, paint with a bold type oil marker on the coating film so that the area is 1 cm ² or more, let stand for 1 minute, hang IPA of about 1 cc, lift the marker ink, and gently wipe all the ink with tissue paper It was. The change in the color difference before and after this stain resistance test was evaluated by a color difference meter (color computer: SM-T45, manufactured by Suga Test Instruments Co., Ltd., measurement hole 12 mm), 45-0 method. Table 4 shows the evaluation results of the stain resistance test.

4) Urethane (meth) acrylate coating film surface hardness (pencil hardness test)
Pencil hardness was measured as an evaluation method of hardness, which is an index of ease of scratching the coating film. Using the composition shown in Table 3, a polycarbonate plate having a thickness of about 2 mm, a width of 100 mm, and a length of 150 mm was coated with an applicator so that the film thickness after curing was about 20 μm, and a UV irradiator (Oak Manufacturing Co., Ltd., Handy UV). -300) was UV photopolymerized at an illuminance of 800 mJ / W to obtain a cured coating film. The resulting cured coating film was measured for pencil hardness according to JIS K-5600. The evaluation results are shown in Table 5.

5) Cured product chemical resistance A chemical resistance test was conducted to examine the resistance to chemical substances used on a daily basis. 5% sodium hydroxide solution is dropped onto the surface of the cured coating film obtained by the same operation as in 4) above so that it has a diameter of 1 to 2 cm and left at a temperature of 23 ° C. for 24 hours. After washing with water, changes in the appearance of the cured coating film were confirmed. The presence or absence of a change was visually determined as no change = ◯ (good) and change = × (poor). The evaluation results are shown in Table 5.

6) Appearance of cured coating film The surface of the coating film obtained by the same operation as in 4) above was visually observed. The case where fine irregularities such as orange peel were observed was judged as x (bad), the case slightly recognized as Δ, and the case not recognized as good (good). The evaluation results are shown in Table 5.
7) Impact resistance As an evaluation of the flexibility and toughness of the coating film, and to evaluate the difficulty of cracking and peeling of the coating film due to impact that directly affects durability, a DuPont impact resistance tester is used. Using. Set a 1/4 inch striker on the cured coating obtained by the same operation as in 4) above, drop a 500 g weight from the specified height, and crack the coating or lift the coating. The presence or absence was confirmed visually. The maximum height (cm) at which no cracking of the coating film or lifting of the coating film was observed was shown as impact resistance. The evaluation results are shown in Table 5.

8) Acetone insoluble matter (gel fraction)
The gel fraction was measured about the cured coating film obtained by the same operation as said 4). First, using the formulation shown in Table 3, an applicator was applied onto a tin plate so that the film thickness after curing was about 50 μm, and UV photopolymerization was performed at an energy of 800 mJ / W to obtain a cured coating film. After the film-like coating film was peeled off, it was immersed in acetone at a temperature of 23 ° C. for 24 hours, the weight before and after the immersion was measured, and the acetone insoluble matter was determined by the following calculation. The evaluation results are shown in Table 6.
Gel fraction (%) = (weight after acetone immersion) / (weight before acetone immersion) × 100

9) Abrasion resistance test The abrasion resistance of the cured coating film obtained by the same operation as in 4) above was evaluated according to the JIS K5600 wear wheel method (wear wheel CS-10, weight 500 g, 500 rotations). Table 6 shows the results of weight loss measurement in the test.

10) Analysis of urethane (meth) acrylate The coating obtained by using the polycarbonate diol raw material urethane (meth) acrylate of the present invention exhibits excellent adhesion and stain resistance, but the UV coating agent is a polycarbonate diol raw material urethane ( Confirmation of whether or not (meth) acrylate is used is carried out by performing fractionation by molecular weight using preparative GPC as necessary, and then (A) binding state analysis by FT-IR (B) pyrolysis gas chromatograph This can be confirmed by conducting a compositional analysis. The conditions are as follows.

(A) FT-IR:
The analytical instrument is not particularly limited, but JASCO FT / IR-4200 is used. If necessary, preparative GPC is used, and the fraction other than the fraction corresponding to the acrylate monomer is used for the analysis. The obtained fraction is applied to a rock salt plate and the presence or absence of a sharp peak of 1250 cm −1 carbonate-bound CO is confirmed.

(B) Pyrolysis GC / MS measurement conditions:
The analysis conditions and apparatus are not particularly limited, but analysis is performed with the following apparatus and conditions using the same fraction as in (A).
Thermal decomposition apparatus: FRONTER LAB 2020D
Heating temperature: 600 ° C
GC / MS equipment: JEOL AutomassSUN
Column: DB-1 (0.25 mm id × 30 m) liquid phase thickness 0.25 μm
Column temperature: 40 ° C. (5 min) → (20 ° C./min temperature increase) → 300 ° C. (12 min hold)
Inlet temperature: 320 ° C
Injection method: Split method (split ratio 1/50)
Interface temperature: 300 ° C
Ion source: EI, temperature 240 ° C., PM = 360V

The composition of Formulation Example 1 was analyzed by the above method. The composition was not fractionated by GPC, and IR analysis was performed as it was. As a result, a bond peculiar to the carbonate group was confirmed at a portion of 1250 cm ⁻¹ . Similarly, as a result of analysis by pyrolysis GC, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, isophorone diisocyanate, pentanediol, pentanediol-derived C5 compound and hexanediol were detected as components. As a result of examining the blending ratio of pentanediol and hexanediol by comparing the known PCDs having a blending ratio of 1,5-pentanediol and 1,6-hexanediol, the ratio was 53:47. From the above results, the effectiveness of this analysis method was confirmed.

Molded product evaluation example As a blended composition, a blended composition was prepared at a ratio shown in Table 7. Molding was performed in a glass petri dish having a diameter of 10 cm, and the blended composition was poured so that the cured thickness was 2 mm, and UV photopolymerization was performed with an energy of 1500 mJ / cm ² to obtain a cured molded product.

1) Hardened Product Hardness Using a Shore D hardness meter, the hardness of the cured molded product of the molded product blending example 1, molded product blended comparative example 1, and molded blended comparative example 2 was measured. Table 8 shows the measurement results.

2) Appearance of cured coating film The surfaces of the cured molded products of the molded product blending example 1, molded product blended comparative example 1 and molded blended comparative example 2 were visually observed. A sample in which fine irregularities such as an orange peel were observed was judged as x (defect), and a sample that was not recognized was judged as good (good). The evaluation results are shown in Table 8.

  The predetermined urethane (meth) acrylate in the present invention can exhibit excellent adhesion, stain resistance, chemical resistance, hydrolysis resistance, flexibility, and abrasion resistance, and includes the urethane (meth) acrylate. It was found that a cured product obtained from a practical composition has excellent durability.

  Urethane (meth) acrylates made from polycarbonate diol obtained in the present invention satisfy various physical properties such as high adhesion, stain resistance, chemical resistance, hydrolyzability, flexibility, and wear resistance at a high level. Can be obtained without the need for an excessive dilution solvent, and can provide a cured product with an excellent appearance. Various coating applications such as painting and adhesives, specifically high appearance and high durability are required. It can be suitably used for various mobile devices, films, architectural interior / exterior and automobile interior / exterior applications. Further, it can be suitably used for cured molded products such as UV cured lenses.

Claims (16)

An isocyanate compound (a) having at least two isocyanate groups, a polycarbonate diol (b) comprising a repeating unit represented by the following general formula (A) and a terminal hydroxyl group, a hydroxyl group-containing (meth) acrylate (c), Wherein the polycarbonate diol (b) comprises a repeating unit represented by the following formula (B) and a repeating unit represented by the following formula (C) as essential repeating units. The total of the repeating units represented by the following formula (B) and the following formula (C) is 60 to 100 mol% of the entire repeating units represented by the general formula (A), and the following components:
Trimethylolpropane triacrylate 20 parts Urethane (meth) acrylate (as solids) 30 parts n-butyl acetate (total) 52 parts 1-hydroxycyclohexyl phenyl ketone A mixture containing 2 parts is coated on a polycarbonate plate, 800 mJ / cm ^The coating film (film thickness: 20 μm) obtained by irradiating and curing the ultraviolet ray of ² shows no separation in the cross-cut method (JIS-K-5600), and the oily black ink applied to the coating film is isopropyl alcohol. Urethane (meth) acrylate having a color difference (ΔE) before and after removal of 3 or less.

(However, R in the formula represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 12 carbon atoms.)

  The urethane (meth) acrylate according to claim 1, wherein no peeling is observed by the cross-cut method even after the coating film is immersed in warm water at 80 ° C for 4 hours.   The urethane (meth) acrylate according to claim 1 or 2, wherein the polycarbonate diol (b) has a primary terminal OH ratio of 95.0 to 99.5%.   The urethane (meth) acrylate according to any one of claims 1 to 3, wherein the polycarbonate diol (b) has a molecular weight of 900 to 1100.   The ratio of the direct adduct of the isocyanate compound (a) and the hydroxyl group-containing (meth) acrylate (c) generated during the reaction for obtaining the urethane (meth) acrylate is 0. 0% with respect to the entire product obtained by the reaction. The urethane (meth) acrylate according to any one of claims 1 to 4, which is 1 to 12% by weight.   The compounding composition containing the urethane (meth) acrylate as described in any one of Claims 1-5, and other (meth) acrylic acid ester. Furthermore, the compounding composition of Claim 6 containing a polymerization initiator. An isocyanate compound (a) having at least two isocyanate groups, a repeating unit represented by the following general formula (A) and a terminal hydroxyl group, and a repeating unit represented by the following formula (B) as an essential repeating unit; The repeating unit represented by the following formula (C), the total of the repeating unit represented by the following formula (B) and the repeating unit represented by the following formula (C) is the total of the repeating units represented by the general formula (A). A hydroxyl group-containing urethane is obtained by reacting with a polycarbonate diol (b) having a primary terminal OH ratio of 95.0 to 99.5% by reaction with a polycarbonate diol (b) of 60 to 100 mol% to obtain a prepolymer of both terminal isocyanate groups. A method for producing urethane (meth) acrylate, comprising a step of further reacting (meth) acrylate (c).

(However, R in the formula represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 12 carbon atoms.)

  The method for producing a urethane (meth) acrylate according to claim 8, wherein the polycarbonate diol (b) has a molecular weight of 900 to 1100.   The coating material containing the urethane (meth) acrylate as described in any one of Claim 1 to 5.   The molding material containing the urethane (meth) acrylate as described in any one of Claim 1 to 5.   A coating material comprising the blend composition according to claim 6 or 7.   The coating material of Claim 10 or 12 used as a coating use with respect to the resin which consists of a polycarbonate resin or the composite material of a polycarbonate and ABS.   The molding material containing the compounding composition of Claim 6 or 7.   A coating material, wherein the coating material according to claim 10 or 12 is coated on a polycarbonate resin or a resin composed of a composite of polycarbonate and ABS.   The coating material according to claim 15, which is one of a mobile phone, a smart phone, a portable music player, a personal computer housing, and a protective cover and a protective film thereof, which are called mobile devices.