JPH08134015A - Methylnorbornene (meth)acrylate, its production and photosensitive resin composition - Google Patents

Abstract

PURPOSE: To obtain a new methylnorbornene (meth)acrylate, having a low shrinkage factor in curing, high diluting properties of blends and useful as a curing component for electron radiation curing type inks, coatings or adhesives, etc. CONSTITUTION: A methylnorbornene (meth)acrylate of formula I (R is H or methyl), e.g. a compound of formula II. This compound of formula I is obtained by reacting propylene with dicyclopentadiene, providing methylnorbornene and then reacting the resultant compound with (meth)acrylic acid in the presence of an acidic catalyst. Although the compound of formula I can be used as a curing component in compositions such as various inks, coatings or adhesives, it is preferably used as the curing component of photosensitive resin compositions. The compound of formula I is preferably blended in an amount of 10-70wt.% in the whole composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to methylnorbornene (meth) acrylate and a method for producing the same, and a photosensitive resin composition. More specifically, it is a novel compound, which is an ultraviolet or electron beam curable ink, paint or The present invention relates to methylnorbornene (meth) acrylate useful as a curing component of an adhesive, a method for producing the same, and a photosensitive resin composition containing the methylnorbornene (meth) acrylate.

[0002]

2. Description of the Related Art Conventionally, various acrylic acid or methacrylic acid esters have been used as a curing component in ultraviolet ray or electron beam curing type inks, paints or adhesives. However, when these conventional esters are used as a curing component in ultraviolet or electron beam curing type inks, paints, adhesives, etc., shrinkage during curing has been one problem. That is, when a curing component is mixed with ink, paint or adhesive and cured by ultraviolet rays or electron beams to form a layer having a desired thickness or shape, the density of the mixture before and after curing When there is a difference in the thickness and the like, and shrinkage occurs, it is not known what thickness and shape the resin has after curing, which is an unstable factor in manufacturing a product. Further, due to the shrinkage of the compound (composition), the original performance as an ink, a paint or an adhesive may be impaired.

In order to solve these problems, acrylic acid or methacrylic acid ester having various bulky substituents, for example, the following formula (II)

Embedded image [In the formula, R represents a hydrogen atom or a methyl group. ] Or the following formula (III)

[0004]

Embedded image [In the formula, R represents a hydrogen atom or a methyl group. ] The compound represented by is used and sold. However, these acrylic acid or methacrylic acid esters have a satisfactory performance with respect to the dilution performance of the compound, which is another performance required as a curing component for ultraviolet ray or electron beam curing type inks, paints or adhesives. Did not have.

On the other hand, the following formula (IV)

[Chemical 4] The compound represented by is a known substance registered as CAS-No. 10027-06-2. However, the above general formula (I)
The compound represented by has not been known yet.

[0006]

SUMMARY OF THE INVENTION The present invention overcomes the drawbacks of the prior art and has a low shrinkage factor when the compound is cured by ultraviolet rays or electron beams and a high dilutability of the compound. To provide a (meth) acrylic acid ester useful as a curing component for an electron beam curable ink, paint or adhesive, a method for producing the ester, and a photosensitive resin composition containing the ester. It was done for the purpose.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that methylnorbornene (meth) acrylate is a novel compound and has a low shrinkage rate during curing. , And high compound dilutability,
It has been found that it is useful as a curing component for inks, paints, adhesives and the like of ultraviolet or electron beam curing type. The present invention has been completed based on such findings. That is, the present invention has the general formula (I)

[0008]

Embedded image [In the formula, R represents a hydrogen atom or a methyl group. ] The methyl norbornene (meth) acrylate represented by these is provided. Further, the present invention is characterized in that after producing methylnorbornene by reacting propylene with dicyclopentadiene, the methylnorbornene is reacted with (meth) acrylic acid in the presence of an acid catalyst. The present invention provides a method for producing methylnorbornene (meth) acrylate represented by I). Further, the present invention also provides a photosensitive resin composition containing the methylnorbornene (meth) acrylate represented by the general formula (I). . Hereinafter, the present invention will be described in detail.

The methylnorbornene (meth) acrylate (correctly, methylnorbornene acrylate or methylnorbornene methacrylate) of the present invention has the general formula (I)

[Chemical 6] It is represented by. In the above general formula (I), R
Represents a hydrogen atom or a methyl group.

The methylnorbornene (meth) acrylate of the present invention having such a structure is a novel compound, has a low shrinkage factor at the time of curing and a high compound dilutability, and is of an ultraviolet or electron beam curing type. It is preferably used as a curing component for inks, paints, adhesives and the like.

Methyl norbornene (meth) according to the present invention
Acrylate can be produced by various methods, but in order to obtain a (meth) acrylic acid ester having excellent performance as a curing component such as ultraviolet ray or electron beam curing type ink, paint or adhesive, It is preferable to manufacture by the method of. That is, in order to produce the methylnorbornene (meth) acrylate represented by the general formula (I) of the present invention, propylene is reacted with dicyclopentadiene to produce methylnorbornene, and then the methylnorbornene is treated with an acid. It is preferably produced by reacting with (meth) acrylic acid in the presence of a catalyst.

In the production method of the present invention, first, propylene is reacted with dicyclopentadiene to produce methylnorbornene. The synthesis by the Diels-Alder reaction can be carried out by either a batch system or a flow system. it can. As the reaction conditions, the molar ratio of the amount of propylene / the amount of dicyclopentadiene is 1 to 10, preferably 4 to 6 in the batch system, and 1 to 20, preferably 5 to 15 in the flow system. The reaction temperature is 160 ° C. to 280 ° C., preferably 180 ° C. to 2 ° C. in the batch system.
It is in the range of 40 ° C, 200 ° C to 350 ° C in the flow system,
It is preferably in the range of 250 ° C to 350 ° C.

Next, the produced methyl norbornene is reacted with (meth) acrylic acid in the presence of an acid catalyst to produce methyl norbornene (meth) acrylate represented by the general formula (I). As reaction conditions, the molar ratio of methylnorbornene amount / (meth) acrylic acid amount is 0.6 to 2.
It is 0, preferably in the range of 0.8 to 1.5. The reaction temperature is in the range of 50 ° C to 100 ° C, preferably 60 ° C to 80 ° C. Examples of the acid catalyst include Lewis acids such as BF ₃ ; mineral acids such as HCl and H ₂ SO ₄ ; organic acids such as p-toluenesulfonic acid; heteropoly acids such as phosphotungstic acid;
A strongly acidic ion exchange resin or the like is used. Further, in this reaction, it is preferable to add a polymerization inhibitor, and as the polymerization inhibitor, hydroquinone, p-methoxyphenol, phenothiazine, copper salt and the like are used.
The amount of the polymerization inhibitor added is 0.01 to 0.5% by weight based on the total amount of methylnorbornene and (meth) acrylic acid.
It is preferred that After the reaction, the catalyst is neutralized with an alkaline aqueous solution and washed with water, and then the low boiling point is distilled off. Further, by performing distillation under reduced pressure, higher purity methylnorbornene can be obtained. When a heteropoly acid is used as the acid catalyst, before neutralization with an alkaline aqueous solution,
It is preferable to put the reaction solution in a hydrocarbon solvent to precipitate and filter the heteropolyacid. When a strongly acidic ion exchange resin is used as the acid catalyst, the resin is filtered off before neutralization with an alkaline aqueous solution.

According to the method for producing methylnorbornene (meth) acrylate according to the present invention as described above, it has excellent performance as a curing component such as ultraviolet ray or electron beam curing type ink, paint or adhesive. The acrylic ester can be efficiently produced.

Further, the methylnorbornene (meth) acrylate of the present invention can be used as a curing component of a composition (formulation) such as various inks, paints or adhesives, but it is a curing component of a photosensitive resin composition. It is preferable to use as. That is, the photosensitive resin composition of the present invention is a composition comprising a material used for an ink, a paint, an adhesive or the like, and the methylnorbornene (meth) acrylate represented by the general formula (I). Yes, it contains the methylnorbornene (meth) acrylate in a fixed ratio as a curing component. The amount of this methylnorbornene (meth) acrylate is not particularly limited, but preferably 5 to 90% by weight in the total composition, more preferably 10 to 10% in the total composition.
It is contained in an amount of 70% by weight. The photosensitive resin composition of the present invention is made of a material widely used in inks, paints, adhesives and the like in addition to the methylnorbornene (meth) acrylate, and its type is not particularly limited, but specifically, Epoxy acrylate, urethane acrylate, polyester acrylate, etc. can be mentioned. Further, in such a photosensitive resin composition, a photosensitizer and the like may be blended in order to efficiently perform ultraviolet ray or electron beam curing.

[0016]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 910 parts by weight of dicyclopentadiene, 115 of propylene
8 parts by weight reactor with an internal capacity of 10 liters (maximum pressure is 1
03 kg / cm ² G), 240 ° C with stirring
The temperature was raised to 180 ° C., and this temperature was maintained for 180 minutes to continue stirring. Then, after cooling to purge excess propylene,
The product was extracted to obtain crude methylnorbornene. This is distilled under reduced pressure, and a fraction of 75 to 76 ° C./5 mmHg is reduced to 10
30 parts by weight were obtained. Next, stirrer, temperature controller, thermometer,
A reactor equipped with a cooling tube, a dropping funnel, and an air introduction tube was charged with 72 parts by weight of acrylic acid, 3 parts by weight of phosphotungstic acid, and 0.2 parts by weight of p-methoxyphenol, and the temperature was raised to 70 ° C while bubbling air. Warm up to 70
While maintaining at ℃, 98 parts by weight of methyl norbornene, 60
It was dripped over a period of minutes. Next, this reaction solution was heated at 70 ° C. for 120 minutes while bubbling with air, and then cooled. Then, all of the cooled reaction solution was dissolved in 840 parts by weight of n-hexane, the precipitated phosphotungstic acid was filtered off, neutralized with a 10% by weight sodium hydroxide aqueous solution, and an aqueous layer was separated, followed by an oil layer. Was washed with water and dried, and n-hexane was distilled off with a rotary evaporator to obtain a reaction product. Furthermore, this is distilled under reduced pressure, 92-95 ° C / 11.5m
98 parts by weight of a fraction of mHg was obtained.

The result of gas chromatography analysis (GC analysis) of the obtained reaction product is shown in FIG. From this GC analysis, nine peaks were confirmed. The GC analysis was carried out using a column: BB-5; φ0.25 mm; 3
0 m, column temperature: initial temperature 40 ° C; 5 minutes later 10 ° C
/ Min to 280 ° C, Inj temperature: 280 ° C,
Carrier gas: Helium: Speed about 1.0 ml / min,
The sample injection volume was 0.2 μl. The obtained reaction product was subjected to mass spectrometry, and as a result, the molecular weight of all nine peaks detected by the above GC analysis was 180. The obtained reaction product has a specific gravity of 0.9 at 25 ° C.
98 g / cm ³ , viscosity at 25 ° C is 3.75 mPa ·
and the elemental analysis values were as follows. The values in parentheses are theoretical values. C: 72.3% (73.3%) H: 9.0% (8.9%) O: 18.7% (17.8%)

Further, the infrared absorption spectrum (IR spectrum) of the obtained reaction product is shown in FIG. The attribution of the spectrum is as follows. ν _CH 2957 cm ^-1 , 2872 cm ^-1 (C-H expansion and contraction) ν _{C = O} 1724 cm ^-1 (C = O expansion and contraction) ν _{C = C} 1620 cm ^-1 (C = C expansion and contraction) ν _CH 1454 cm ^-1 (C-H) Bend)

The results of ¹ H-NMR spectrum are shown in FIG. 3 and the results of ¹³ C-NMR spectrum are shown in FIG. The attribution of each spectrum is as follows according to the structural formula of the following formula (IV). ¹ H-NMR spectrum (270 MHz: CDCl ₃ );
δ (ppm) 0.80 to 2.20 ppm (H2, H3, H4, H5, H7, H8,12H) 4.60 (H6,1H) 5.72 (H11a, 1H) 6.07 (H10,1H) 6.32 (H11b, 1H) ¹³ C-NMR spectrum (67.4 MHz: CDC
l ₃ ); δ (ppm) 16.17 (CH ₃ , C8) 30.08 (CH ₂ , C7) 32.95 (CH ₂ , C2) 30.08 (CH, C4) 41.16 (CH ₂ , C5) 41.41 (CH ₂ , C3) 46.77 (C, C1) 79.45 (CH, C6) 129.12 (CH, C10) 129.66 (CH ₂ , C11) 165.54 (C = O, C9)

From these analysis results, the obtained reaction product is a compound of the present invention represented by the following formula (IV):
It was found to be one component of methylnorbornene acrylate.

[Chemical 7] The numerical values 1 to 11 and the letters a and b in the formula are numbers assigned to each atom when the spectrum is assigned. The peak with a molecular weight of 180 obtained by GC analysis is considered to be 8 isomers of methylnorbornene acrylate, that is, 2 structural isomers and 4 stereoisomers.

Examples 3 to 4 Methyl norbornene acrylate 4 obtained in Example 1
0 part by weight and 5 parts by weight of a photosensitizer (Irgacure 184) were mixed with 60 parts by weight of the oligomer shown in Table 1 to prepare a composition, and the viscosity of this composition at 25 ° C. was measured. The results are shown in Table 1. Further, this mixture was applied on a glass plate so as to have a thickness of 1 mm, and was ultraviolet-cured with a high pressure mercury lamp (500 mJ / cm ² ), and the shrinkage ratio was determined from the difference in density of the mixture before and after curing. The result is first
Shown in the table.

[0023]

[Table 1] As can be seen from Table 1, the methylnorbornene acrylate of the present invention was found to have a low shrinkage rate upon curing of the formulation.

[0024]

EFFECT OF THE INVENTION The methylnorbornene (meth) acrylate of the present invention is a novel compound, which has a high dilutability of the composition, facilitates the handling of the composition, and can be used as a paint, ink or adhesive by ultraviolet rays or electron beams. When the composition such as the agent is cured, the shrinkage of the composition can be suppressed to a low level. Therefore, the methylnorbornene (meth) acrylate of the present invention is extremely useful as a curing component for paints, inks, adhesives and the like by ultraviolet rays or electron beams and has a high industrial utility value. Further, according to the method for producing methylnorbornene (meth) acrylate of the present invention, methylnorbornene (meth) acrylate can be efficiently produced.

[Brief description of drawings]

FIG. 1 is a chart showing the results of a GC spectrum of methylnorbornene acrylate obtained in Example 1.

FIG. 2 is a chart showing the results of IR spectrum of methylnorbornene acrylate obtained in Example 1.

FIG. 3 is a chart showing the ¹ H-NMR spectrum results of the methylnorbornene acrylate obtained in Example 1.

FIG. 4 is a chart showing the results of ¹³ C-NMR spectrum of methylnorbornene acrylate obtained in Example 1.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroaki Yashima 1 Shingu Town, Tokuyama City, Yamaguchi Prefecture Idemitsu Petrochemical Co., Ltd.

Claims (3)

[Claims] 1. A compound of the general formula (I) [In the formula, R represents a hydrogen atom or a methyl group. ] The methyl norbornene (meth) acrylate represented by these. 2. The method according to claim 1, wherein after producing methylnorbornene by reacting propylene with dicyclopentadiene, the methylnorbornene is reacted with (meth) acrylic acid in the presence of an acid catalyst. A method for producing methylnorbornene (meth) acrylate. 3. A photosensitive resin composition containing the methylnorbornene (meth) acrylate according to claim 1.