JP2003307849A - Three-dimensional pattern having adhesiveness and method for forming the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a three-dimensional pattern having adhesiveness, retaining adhesiveness after pattern formation, capable of adhering to another substrate in a final curing process by irradiation with a high energy beam or by heating, and giving a finally cured pattern exhibiting very high heat-, water- and solvent resistances and very high dimensional stability. <P>SOLUTION: The three-dimensional pattern consists of a half cured photosensitive resin composition containing (A) a compound having a ring-opening polymerizable reactive group in its molecule and (C) a compound which absorbs a high energy beam and generates an acid or a base as essential components. The minimum size of the pattern is ≤50 μm, the height is 1 μm to 1 mm and the surface tack of the pattern is ≥98 N/m. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a three-dimensional pattern having adhesiveness and a photosensitive resin composition giving the same. More specifically, it is possible to retain the adhesiveness after pattern formation, and then to bond with another substrate in the process of final curing by irradiation with high energy rays or heating, and the final cured product has good physical properties, The present invention relates to a three-dimensional pattern having adhesiveness useful for electronic materials and the like.

[0002]

2. Description of the Related Art Conventionally, a printing method such as screen printing or gravure printing has been used as a method for forming a pattern of an adhesive layer on a substrate. However, with this printing method, it is difficult to form a fine pattern having a size of 50 μm or less, and it is difficult to control the film thickness within several μm and to secure the alignment accuracy within several μm. In addition, it is impossible to keep the adhesiveness of the obtained pattern after patterning the adhesive layer, according to the conventional thinking. For example, when the photocurable epoxy resin used when making a build-up substrate is irradiated with light to be cured and patterned after the development process, first, it is uncured by contacting with a commonly used organic developer. Although the part can be removed, the adhesiveness of the pattern part is significantly reduced. Even if the irradiation amount of high energy rays is reduced and the adhesiveness is improved, even in the developing step, even the hardened portion is removed and it becomes difficult to form a pattern.

According to the conventional premise of the developing process,
The direction in which the photosensitive resin composition is irradiated with high energy rays to be cured to form a pattern is opposite to the direction in which the adhesiveness is maintained. Further, the adhesive pattern is required to have characteristics such as high heat resistance after curing, water resistance, solvent resistance, and dimensional stability, but in a commonly used radical curable adhesive, It was difficult to meet these required performances.

[0004]

In order to solve the above problems, the present invention can form a fine pattern, can maintain high adhesiveness even after the pattern is formed, and can irradiate high energy rays again. It is possible to adhere to another substrate during the final curing process by heating or by heating, and the final cured product has good physical properties, and a three-dimensional pattern having adhesiveness useful for electronic materials and the formation thereof. It provides a method.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have paid attention to a ring-opening polymerizable compound having a relatively slow curing reaction rate, and have keenly sought a method for maintaining adhesiveness even after a three-dimensional pattern is formed. As a result of examination, the photosensitive resin composition is a low-viscosity compound that absorbs high energy rays and undergoes ring-opening polymerization, and particularly (A) a ring-opening polymerizable compound having a ring-opening polymerizable reactive group in the molecule and ( A photosensitive resin composition comprising as an essential component C) a compound capable of absorbing an actinic ray to generate an acid or a base, and preferably (B) an ethylenically unsaturated compound having an ethylenically unsaturated bond in the molecule. Particularly preferably, the component (A) is (1) a compound having an epoxy group or an oxetane group as a ring-opening polymerizable reactive group,
A compound having two or more ring-opening polymerizable reactive groups in the molecule, wherein the component (B) is added to 100 parts by weight of the component (1),
(2) 1 to 100 parts by weight of an ethylenically unsaturated compound having a hydroxyl group and an ethylenically unsaturated bond in the molecule at the same time, and (3) an ethylenically unsaturated compound having no hydroxyl group in the molecule and having 2 or more ethylenically unsaturated bonds. By using a photosensitive resin composition characterized by comprising 1 to 100 parts by weight of a saturated compound, a high adhesive force, a pattern with a fine dimension can be formed, and the final cured product has high heat resistance and water resistance. The inventors have found that it is possible to form a three-dimensional pattern having solvent resistance, dimensional stability, and adhesiveness, and completed the present invention.

That is, the present invention is as follows. 1. A semi-cured photosensitive resin composition comprising (A) a compound having a ring-opening polymerizable reactive group in the molecule and (C) a compound that absorbs a high energy ray and generates an acid or a base as essential components. A three-dimensional pattern having a minimum dimension of 50 μm or less and a height of 1 μm or more and 1 m
A three-dimensional pattern having an adhesiveness of m or less and a tack of the surface of the three-dimensional pattern of 98 N / m or more.

2. A liquid photosensitive resin composition layer containing, on a substrate, (A) a compound having a ring-opening polymerizable reactive group in the molecule and (C) a compound that absorbs a high energy ray and generates an acid or a base as essential components Is formed into a semi-cured state by irradiating the whole surface with a high energy ray, and then a part of the semi-cured adhesive layer is removed by a laser to form a pattern, which has an adhesive property. A three-dimensional pattern forming method.

3. A liquid photosensitive resin composition layer containing, on a substrate, (A) a compound having a ring-opening polymerizable reactive group in the molecule and (C) a compound that absorbs a high energy ray and generates an acid or a base as essential components Is formed into a semi-cured state by irradiating a part of it with a high energy ray, and then the liquid photosensitive resin composition in the unirradiated portion of the high energy ray is removed to form a pattern. A method for forming a three-dimensional pattern having adhesiveness.

4. A photosensitive resin composition comprising (A) a compound having a ring-opening polymerizable reactive group in the molecule and (C) a compound capable of absorbing a high energy ray to generate an acid or a base, which is at 20 ° C. A three-dimensional pattern-forming photosensitive resin composition having adhesiveness, which has a viscosity of 1 mPa · s or more and 5000 mPa · s or less.

5. Furthermore, (B) contains an ethylenically unsaturated compound having an ethylenically unsaturated bond in the molecule, (B)
3. The component is 2 to 200 parts by weight with respect to 100 parts by weight of the component (A), and the component (C) is contained in an amount of 0.1 to 10 wt% with respect to the total weight of the components (A) and (B). A photosensitive resin composition for three-dimensional pattern formation, which has the adhesiveness described above.

6. The component (A) is a compound having (1) one or more ring-opening polymerizable reactive groups selected from an epoxy group or an oxetane group in the molecule, and the component (B) is
To 100 parts by weight of component (A), 1 to 100 parts by weight of (2) an ethylenically unsaturated compound having a hydroxyl group and an ethylenically unsaturated bond in the molecule at the same time, and (3) ethylene having no hydroxyl group in the molecule 4. 1 to 100 parts by weight of an ethylenically unsaturated compound having two or more polyunsaturated bonds. A photosensitive resin composition for three-dimensional pattern formation, which has the adhesiveness described above.

7. A cured product obtained by irradiating a three-dimensional pattern having adhesiveness as described in 1 above with a high energy ray or applying heat.

8. The above 1. A structure, which is formed by adhering another base material on the three-dimensional pattern having adhesiveness described in 1) by applying high energy rays or heating while applying pressure.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to its preferred embodiments. The adhesive three-dimensional pattern of the present invention comprises a semi-cured photosensitive composition. The semi-cured state means a cured state before reaching a finally cured state. Therefore, the hardness (Shore D hardness (0
Sec)) is H _D0 , the hardness H _{D in the} semi-cured state is
Defined as _{0.1H D0 ≦ H D ≦ 0.9H D0} . A more preferable range of the semi-cured state is 0.2H _D0 ≤ H _D ≤ 0.8H _D0
And a more preferable range is 0.3H _D0 ≦ H _D ≦ 0.
Is a 7H _D0.

When removing the uncured portion which is not irradiated with high energy rays, up to the semi-cured portion is removed, and when another substrate is bonded in the subsequent step, the uncured material is not cured. From the viewpoint of preventing bleeding into the produced pattern space, it is preferable that H _D is 10% or more of H _{D 0} . Further, it is preferable that H _D is 90% or less of H _D0 from the viewpoint of expressing a sufficient adhesive force in the subsequent steps.

The adhesive three-dimensional pattern of the present invention is one in which a structure such as fine holes, grooves, or fine protrusions is formed in a photosensitive resin layer, and the pattern has fine dimensions. Is a major feature. Further, patterns having greatly different dimensions may be mixed. The minimum dimension of the three-dimensional pattern is 50 μm or less, preferably 30 μm or less, more preferably 20 μm or less. When the minimum dimension is larger than 50 μm, patterning can be performed by a simpler method such as screen printing. Further, it is preferably 1 μm or more. The minimum dimension of the present invention means, for example, in the case of a groove pattern, the minimum width of the groove formed in the photosensitive resin layer, in the case of a linear pattern, the minimum line width, and in the case of a hole pattern, the photosensitive resin. Refers to the dimension of the smallest portion of the diameter or width of a hole formed in a layer. In the case of independent convex pattern, the convex part is triangular prism, square prism, polygonal prism,
The pattern may be any of a columnar pattern, an elliptic column, or a columnar pattern having an irregular bottom surface, a triangular pyramid, a quadrangular pyramid, a polygonal cone, a cone, an elliptic cone, or the like, and the pattern is formed on the substrate on which the pattern is formed. The diameter of a circle including all shapes projected on parallel planes is defined as the minimum dimension.

The thickness of the adhesive three-dimensional pattern of the present invention is 1 μm or more and 1 mm or less, preferably 5 μm.
m or more and 100 μm or less, more preferably 10 μm or more 1
It is not more than 00 μm. The thickness is 1 μm or more, and the minimum dimension can be easily 50 μm or less in order to secure a sufficient adhesive force when the three-dimensional pattern is bonded to another substrate.
The following are preferred. Further, the surface tack of the adhesive three-dimensional pattern of the present invention is 98 N / m or more, preferably 196 N / m or more, and more preferably 490 N / m or more. The tack is preferably 98 N / m or more in order to secure sufficient adhesive strength when the three-dimensional pattern is adhered to another base material. The tack of the present invention means stickiness. At 20 ° C, the tack is a 1 mm wide aluminum ring with a radius of 50 mm and a width of 13 mm on the smooth part of the sample piece.
Contact the 3mm part, 0.5k to the aluminum ring
After applying a load of g for 4 seconds, the aluminum wheel is pulled up at a constant speed of 30 mm / min, and the resistance force when the aluminum wheel separates from the sample piece is read by a push-pull gauge. The larger this value, the greater the stickiness and the higher the adhesive strength.

Next, the method for forming an adhesive three-dimensional pattern of the present invention will be described. The first method of forming a three-dimensional pattern having adhesiveness of the present invention is to form a liquid photosensitive resin composition layer on the surface of a substrate, and then apply high energy rays to the entire surface of the photosensitive resin composition layer. This is a method in which a curing reaction is caused by irradiation to form a photosensitive resin composition layer in a semi-cured state, and the photosensitive resin composition layer in a semi-cured state is patterned by a laser. The liquid photosensitive resin composition is used because it is possible to follow even minute irregularities on the surface of the base material, and high adhesive strength can be secured due to this characteristic. Although the curing reaction is initiated by irradiating the entire surface of the photosensitive resin composition layer formed on the surface of the substrate with a high energy ray, it is important to keep the semi-cured state without completely curing it. By adjusting the amount of energy of the high-energy rays to be irradiated, a semi-cured state
That is, it is possible to control the tackiness of the surface. The laser used for patterning is not particularly limited, but a carbon dioxide laser,
Lasers having oscillation wavelengths in the infrared region, such as YAG lasers and semiconductor lasers, excimer lasers, second, third, and fourth harmonics of YAG lasers, oscillation wavelengths in the visible or ultraviolet regions, such as metal vapor lasers such as copper vapor lasers. Can be mentioned. Especially 10μ
When forming a fine pattern of m or less, a laser having an oscillation wavelength in the ultraviolet or vacuum ultraviolet region such as the third and fourth harmonics of an excimer laser or a YAG laser is preferable.

The second method of forming a three-dimensional pattern having adhesiveness of the present invention is to irradiate a part of the liquid photosensitive resin composition layer formed on a substrate with a high energy ray. This is a method of forming a pattern by removing the liquid photosensitive resin composition layer in the high energy beam non-irradiated portion after the cured state. The method of irradiating high-energy rays is to irradiate light with a wavelength in the visible or ultraviolet region through a photomask having a light-shielding portion, and to use a photomask that is processed into a beam shape such as laser, electron beam, or ion beam. It is a method of scanning and irradiating without intervention. Examples of the method of removing the portion not irradiated with high energy rays, that is, the liquid adhesive layer include a method of irradiating high pressure gas, a method of irradiating high pressure steam, and a method of irradiating high pressure water.

Next, the liquid photosensitive resin composition used in the present invention will be described. The liquid photosensitive resin composition contains a compound (A) having a ring-opening polymerizable reactive group and a compound (C) that absorbs a high energy ray and generates an acid or a base as essential components. Since the ring-opening polymerization reaction type photosensitive resin composition has a slower reaction rate than the radical polymerization reaction type adhesive and easily forms a semi-cured state, it forms a three-dimensional pattern having adhesiveness of the present invention. It is preferable as a material to be used.

As the ring-opening polymerization-reactive compound (A) of the present invention, an epoxy compound, an oxetane compound, a cyclic ester compound, a dioxolane compound, a spiro orthocarbonate compound, a spiro orthoester compound, a bicycloorthoester compound, a cyclosiloxane compound, Examples thereof include cyclic imino ether compounds, cyclic imine compounds, bicyclic urea compounds, cyclic carbonate compounds, cyclic sulfite compounds, and lactam compounds. The ring-opening polymerizable compound of the present invention has 1 ring-opening polymerizable reactive group in the molecule.
Or more, preferably 2 or more.

Among the ring-opening polymerization-reactive compounds (A), compounds having particularly high reactivity include compounds having two or more epoxy groups such as glycidyl groups and epoxycyclohexyl groups or oxetane groups in the molecule. Further, compounds having two or more epoxy groups or oxetane groups may be used alone or as a mixture. Furthermore,
A compound having both an epoxy group and an oxetane group in the same molecule may be used.

Specific examples of the compound (1) having an epoxy group include compounds obtained by reacting epichlorohydrin with polyols such as various diols and triols,
That is, ethylene glycol diglycidyl ether,
Diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether , 1,6-hexanediol diglycidyl ether,
Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A diglycidyl ether,
Hydrogenated bisphenol A diglycidyl ether, diglycidyl ether of a compound obtained by adding ethylene oxide or propylene oxide to bisphenol A, polytetramethylene glycol diglycidyl ether, poly (propylene glycol adipate) diol diglycidyl ether, poly (ethylene glycol adipate )
Examples thereof include diol diglycidyl ether and poly (caprolactone) diol diglycidyl ether.

As another example, a polyepoxy compound obtained by reacting a compound having two or more ethylene bonds in the molecule with a peracid such as peracetic acid, that is, 3,4-epoxycyclohexylmethyl-3 ', 4. ′ -Epoxycyclohexylcarboxylate, 1-methyl-3,4-epoxycyclohexylmethyl-1′-methyl-3 ′,
4'-epoxycyclohexylcarboxylate, adipic acid bis [1-methyl-3,4-epoxycyclohexyl] ester, vinylcyclohexene diepoxide,
Examples thereof include polyepoxy compounds obtained by reacting polydienes such as polybutadiene and polyisoprene with peracetic acid, epoxidized soybean oil, and the like.

As the oxetane compound used in the present invention, a commonly used compound can be used, and although it is not particularly limited, xylylene dioxetane (trade name "OXT-121" manufactured by Toagosei Co., Ltd. ]),
Examples include 3-ethyl-3-hydroxymethyl oxetane (trade name "OXT-101" manufactured by Toa Gosei Co., Ltd.), trade marks "OXT-221" and "PNOX-1009" manufactured by Toa Gosei Co., Ltd. Among the components (1), 20 ° C
Has a viscosity of 5000 mPa · s or less, more preferably 1000 mPa · s or less, and further preferably 500 mP.
A compound of a · s or less is preferable because good cured product characteristics can be obtained. This factor is not clear at present, but it is presumed that the degree of freedom of molecular mobility is large.

Other examples of the cyclic ester compound used in the present invention include compounds having an ε-caprolactone ring, a γ-butyrolactone ring and a β-propionlactone ring. Further, compounds having different ring-opening polymerizable reactive groups in one molecule may be used. Further, in the present invention, particularly in the case of a compound having a ring-opening polymerizable reactive group and an ethylenically unsaturated bond at the same time in the molecule, it is included in the ring-opening polymerizable reactive compound. These can be used alone or in combination.

The amount ratio of the ethylenically unsaturated compound (B) having an ethylenically unsaturated bond used in the present invention is in the range of 2 to 200 parts by weight with respect to 100 parts by weight of the ring-opening polymerizable compound (A). is there. From the viewpoint of thick film curability of the composition, 2 parts by weight or more is preferable, and from the viewpoint of mechanical properties of the cured product obtained, 100 parts by weight or less is preferable. Further, as the ethylenically unsaturated compound (B) of the present invention, particularly an ethylenically unsaturated compound (2) having a hydroxyl group and an ethylenically unsaturated bond at the same time in the molecule
And an ethylenically unsaturated bond with 2 hydroxyl groups in the molecule
A combination of the above ethylenically unsaturated compounds (3) is preferable. Therefore, a particularly preferable combination is a combination of the epoxy compound (1), the ethylenically unsaturated compound (2), the ethylenically unsaturated compound (3) and the compound (C) which absorbs actinic rays and generates an acid. .

Among the ethylenically unsaturated compounds (2) having a hydroxyl group and an ethylenically unsaturated bond in the molecule which can be used in the present invention, a compound having a hydroxyl group and methacrylic acid or a hydroxyl group and an acryloyl group at the same time is preferable. Examples of the compound (2) include polyoxyethylene glycol monomethacrylate, polyoxyethylene glycol monoacrylate, polyoxypropylene glycol monomethacrylate, and polyoxypropylene glycol monoacrylate.

These can be used alone or in combination. In the present invention, the molecular weight of these unsaturated compounds (2) is preferably 200 or more.
When the molecular weight is 200 or more, it is possible to obtain a resin having excellent mechanical properties, especially toughness, after photocuring. It is more preferably 300 or more, still more preferably 500 or more. The unsaturated compound (2) is preferably used in the range of 1 to 100 parts by weight based on 100 parts by weight of the compound of the component (1). When this value is 1 or more, the thick film curability of the composition is sufficient, and when it is 100 or less, the obtained cured product has excellent mechanical physical properties. A more preferable range is 5 to 60 parts by weight, and further preferable is 10 to 50 parts by weight.

Among the ethylenically unsaturated compounds (3) having no hydroxyl group in the molecule and having two or more ethylenically unsaturated bonds which can be used in the present invention, a compound having a methacryloyl group or an acryloyl group is preferable. . Examples of the compound (3) include diethylene glycol dimethacrylate and diacrylate, tetraethylene glycol dimethacrylate and diacrylate, propylene glycol dimethacrylate and diacrylate, dipropylene glycol dimethacrylate and diacrylate,
Tripropylene glycol dimethacrylate and diacrylate, butanediol dimethacrylate and diacrylate, hexanediol dimethacrylate and diacrylate, nonanediol dimethacrylate and diacrylate, trimethylolpropane trimethacrylate and triacrylate, dimethacrylate and dimethacrylate having bisphenol skeleton Examples thereof include ethylenically unsaturated compounds having no functional group capable of reacting with an epoxy group such as acrylate.

It is preferable to use 1 to 100 parts by weight of the ethylenically unsaturated compound having 2 or more ethylenically unsaturated bonds in the molecule of (3) with respect to 100 parts by weight of the compound of the component (1). . If this value is larger than 1, the thick film curability of the composition is sufficient, and if it is smaller than 100,
The toughness of the obtained cured product is sufficient. The preferred range is 3
To 60 parts by weight, more preferably 5 to 50 parts by weight. Examples of the compound (C) that absorbs a high energy ray and generates an acid used in the present invention include triarylsulfonium salts, diaryliodonium salts, and aryls having BF ₄ ⁻ , PF ₆ ⁻ , SBF ₆ ^−, etc. as counterions. There are diazonium salts and the like, and commercially available photocationic polymerization initiators such as triarylsulfonium hexafluorophosphate and p-thiophenoxyphenylsulfonium hexafluorophosphate can be used. These have a function of generating an acid such as Lewis acid or Bronsted acid upon irradiation with high energy rays to cause a curing reaction.

From the viewpoint of curability, triarylsulfonium salts are preferable. Among them, triarylsulfonium hexafluorophosphate is excellent in thick film curability. Examples of the compound (C) that absorbs a high energy ray and generates a base used in the present invention include an oxime ester compound that generates a Schiff base, an ammonium compound that generates an amine, a dimethoxybenzyl urethane compound,
A benzoin compound, an orthonitrobenzyl urethane compound, and a compound that generates a hydroxy ion can be used. Further, the photobase generator described in JP-A 2000-330270 can be used.

The compound which generates an acid or a base upon irradiation with high energy rays is added in the range of 0.1 to 10% by weight based on the total weight of the components (A) and (B). If this value is more than 0.1% by weight, the curability of the resin is sufficient, and if less than 10% by weight, a cured product having a large cured thickness can be easily obtained. From this point of view, the preferable addition amount is 1 to 6% by weight. The photosensitive resin composition of the present invention,
A thermal polymerization initiator that generates an acid or a base by heat can also be added. For example, the trademark "S" manufactured by Asahi Denka Kogyo Co., Ltd.
P-77 "," SP-66 ", Sanshin Chemical Co., Ltd., trademark" S "
"I-60L", "SI-80L", "SI-100L"
And so on. The addition amount is 50 wt% or less, preferably 30 wt% or less, and more preferably 20 wt% or less of the compound (C) that absorbs high energy rays and generates an acid or a base.

In the photosensitive resin composition used in the present invention, the above-mentioned components (A) to (C) may be contained in an amount capable of exerting their effects, but any of the above-mentioned components (A) to (C) is required. If the components are also liquid at room temperature, these components in the form as they are, without using any other solvent or medium, to the extent that the entire predetermined amount of each can be visually confirmed to be uniform. Then, the desired photosensitive resin composition can be obtained by stirring and mixing by a usual method.
Even if any of the components (A) to (C) is solid at room temperature, if the solid components are compatible with other liquid components, the above method is used as it is. The desired photosensitive resin composition can be obtained by stirring and mixing by the same method as described above.

When the solid component and the liquid component are incompatible with each other, or when all the components (A) to (C) are solid at room temperature, for example, at least one solid component is By heating above the melting point, the components are liquefied, and the mixture is stirred and mixed at the temperature in the same manner as the above-mentioned method to obtain the desired photosensitive resin composition. it can.

As described above, in the method of preparing the composition,
When some of the components (A) to (C) are liquid, other solid components are dissolved in the liquid component during the stirring / mixing process.
It may be dispersed. Further, in order to shorten the time until the entire composition becomes uniform, if necessary, a solvent, a plasticizer, etc. are added to the mixture, and the effect of the present invention expected for the intended composition is not impaired. You may add in the range.

In addition to the above, in the photosensitive resin composition of the present invention, in order to adjust the viscosity and the physical properties of the obtained cured product,
Ingredients that are usually added to photosensitive resins may be added as long as they do not affect the achievement of the effects of the present invention. Examples of such additive components include polymers known as liquid photosensitive resins such as unsaturated polyurethane and unsaturated polyester, isobornyl acrylate and methacrylate, cyclohexyl acrylate and methacrylate, benzyl acrylate and methacrylate, phenyl acrylate and methacrylate, and other epoxy groups. Examples thereof include ethylenically unsaturated compounds having no functional group capable of reacting with, ultraviolet absorbers and storage stabilizers.

Among the above-mentioned additional components, the unsaturated polyurethane is obtained by first reacting a diol compound with a diisocyanate compound to obtain a polyurethane, and then adding a hydroxyl group- or amino group-containing ethylenically unsaturated compound or an isocyanate group-containing ethylenic unsaturated compound to the polyurethane. It is obtained by reacting a saturated compound. The diol compound for obtaining the above-mentioned polyurethane has two hydroxyl groups in one molecule.
Such as polyester diol such as polypropylene glycol adipate diol, polyneopentyl glycol adipate diol, polybutylene glycol adipate diol, polycaprolactone diol, polyvalerolactone diol, polyethylene glycol diol, polypropylene glycol, polytetramethylene glycol, etc. Polyether diol etc. can be mentioned as an example.

The molecular weight obtained from the hydroxyl value of the diol compound is usually about 400 to 5,000.
5 from the perspective of obtaining a softer and stronger polyurethane
It is preferable to use one having a molecular weight of about 00 to 2500. Examples of the diisocyanate compound for obtaining the polyurethane include compounds having two or more isocyanate groups, such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and isophorone diisocyanate. Among these, tolylene diisocyanate is preferred because it does not increase the viscosity of the polyurethane obtained so much and is flexible and easy to obtain.

As the hydroxyl group-containing ethylenically unsaturated compound to be reacted with the above-mentioned polyurethane, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, N-methylol acrylamide, polyoxyethylene glycol monomethacrylate, polyoxypropylene glycol. Monomethacrylate etc. can be mentioned as an example. Of these, hydroxyethyl methacrylate and hydroxypropyl methacrylate are preferable from the viewpoint of flexibility and strength, and hydroxypropyl methacrylate, which has excellent water resistance, is most preferable.

Examples of the isocyanate group-containing ethylenically unsaturated compound that is reacted with the polyurethane include compounds obtained by adding a hydroxyl group-containing ethylenically unsaturated compound and a diisocyanate compound in a ratio of 1: 1. When a hydroxyl group-containing ethylenically unsaturated compound is used in the preparation of unsaturated polyurethane, first, a polyurethane having isocyanate groups at both ends is synthesized by reacting the diol compound with a diisocyanate compound, and this is reacted with a hydroxyl group-containing ethylenically unsaturated compound. In this case, in order to suppress the side reaction and terminate the reaction in a short time, a hydroxyl group-containing ethylenically unsaturated compound is usually added in an excess of about 2 to 5 times equivalent to the polyurethane having isocyanate groups at both ends. It is preferred to obtain a mixture of saturated bond-containing polyurethane and excess hydroxyl-containing ethylenically unsaturated compound.

On the other hand, when an isocyanate group-containing ethylenically unsaturated compound is used in the preparation of unsaturated polyurethane, first, a polyurethane having hydroxyl groups at both ends is synthesized by reacting the above-mentioned diol compound with a diisocyanate compound, and then, an isocyanate group-containing ethylenically unsaturated compound is prepared. React the compound. In this case, the isocyanate group-containing ethylenically unsaturated compound, the number of the isocyanate group is generally added in the same range as the number of hydroxyl groups of the hydroxyl group at both ends or a small number, but facilitates stirring. In order to suppress side reactions, it is preferable to add a component that does not participate in the urethanization reaction as a diluent to reduce the viscosity of the reaction system. When the isocyanate group-containing ethylenically unsaturated compound is excessively added to the polyurethane having hydroxyl groups at both ends, it is preferable to eliminate the excess isocyanate group by adding a compound having active hydrogen such as a hydroxyl group after completion of the reaction.

Further, a polar group such as a carboxyl group can be introduced into the unsaturated polyurethane. The introduction of a carboxyl group into an unsaturated polyurethane is carried out, for example, by adding an ethylenically unsaturated compound containing 2 hydroxyl groups to a polyurethane having isocyanate groups at both ends, and reacting 1 hydroxyl group with an isocyanate group to obtain 2 hydroxyl groups. And an unsaturated polyurethane having two ethylenically unsaturated bonds,
Further, an acid anhydride is added to cause a ring-opening reaction with the hydroxyl group of the polyurethane, whereby an unsaturated polyurethane having both a carboxyl group and an ethylenically unsaturated bond at both ends can be obtained.

Examples of the ethylenically unsaturated compound containing two hydroxyl groups used here include hydroxyl groups bonded to primary and secondary carbons such as compounds obtained by adding water to glycidyl methacrylate or acrylate to open the epoxy group. Can be used. By utilizing the difference in reactivity between the primary carbon-bonded hydroxyl group and the secondary carbon-bonded hydroxyl group, an unsaturated polyurethane having hydroxyl groups at both ends in which only one hydroxyl group in the molecule has reacted with an isocyanate group can be obtained.

Acid anhydrides used for introducing a carboxyl group by ring-opening reaction with a hydroxyl group include succinic acid and
Examples thereof include phthalic anhydride and maleic anhydride. An unsaturated polyester may be used as an additive component instead of the unsaturated polyurethane. The unsaturated polyester is obtained by a dehydration condensation reaction between a diol compound and an ethylenically unsaturated bond-containing dicarboxylic acid compound.
Alternatively, both end hydroxyl groups or both end carboxyl group polyesters are synthesized by a dehydration condensation reaction from a diol compound and a dicarboxylic acid compound, and then an ethylenically unsaturated compound having a functional group capable of reacting with these end functional groups is reacted. You can also get it.

Examples of the diol compound include ethylene glycol, diethylene glycol, polyethylene glycol,
Propylene glycol, polypropylene glycol, butanediol and the like can be mentioned as examples. As the dicarboxylic acid compound, adipic acid, azelaic acid, sebacic acid, isophthalic acid, succinic acid, phthalic anhydride,
Saturated dicarboxylic acids such as terephthalic acid and fumaric acid,
Examples thereof include ethylenically unsaturated dicarboxylic acids such as maleic acid and maleic anhydride.

The number average molecular weight determined by GPC measurement using the unsaturated polyurethane obtained as described above and the polystyrene of the unsaturated polyester as a standard is 80.
It is preferably 0 to 25,000. The smaller the molecular weight, the lower the viscosity of the resulting photosensitive resin composition, but if the molecular weight is smaller than this, the flexibility of the cured product tends to be lost. If the molecular weight is large, the flexibility of the cured product is easily secured, but if it is larger than this, the viscosity of the obtained photosensitive resin composition becomes high, and bubbles are easily entrained.

The upper limit of the viscosity of the photosensitive resin composition containing (A) to (C) of the present invention is 5000 mP at 20 ° C.
a · s or less, preferably 1000 mPa · s or less, more preferably 500 mPa · s or less, particularly preferably 30
It is preferably 0 mPa · s or less, and the lower limit is preferably 1 mPa · s or more, preferably 5 mPa · s or more. When it is greater than 5000 mPa · s, the viscosity is large, it is difficult to remove the unirradiated portion of high energy rays, and it is difficult to follow the fine irregularities on the surface of the base material. On the other hand, when it is less than 1 mPa · s, the physical properties such as strength of the cured product deteriorate.

In the present invention, it is preferable to add a leveling agent to the photosensitive resin composition. The leveling agent used in the present invention is a compound added when the photosensitive resin composition is applied to the surface of a circuit board or an uneven base material so that the surface does not have unevenness. The amount of the leveling agent added is preferably 0.05 wt% or more and 5% or less of the total amount of the compounds (A), (B) and (C). 0.05wt
If it is added in an amount of less than 5%, the smoothness tends to be lowered, and if it is added in an amount of more than 5% by weight, the curability and adhesion of the photosensitive resin composition tend to be lowered. The leveling agent is not particularly limited, but examples thereof include siloxane compounds such as polydimethylsiloxane and polyether-modified polydimethylsiloxane, acrylic polymers, and surfactants.

In order to reduce the viscosity of the photosensitive resin composition used in the present invention, an ethylenically unsaturated compound having a functional group capable of reacting with a ring-opening polymerization reactive compound, or having at least two ethylenically unsaturated bonds is used. This can be performed by increasing the blending ratio of the ethylenically unsaturated compound, particularly the liquid ethylenically unsaturated compound. Among the liquid ethylenically unsaturated compounds, those having a small molecular weight are particularly effective in lowering the viscosity. Adding a compound having a molecular weight of less than 200 and having a hydroxyl group and an ethylenically unsaturated bond at the same time in the molecule in a range that does not deteriorate the physical properties of the cured product also has the effect of decreasing the viscosity. It is also effective to reduce the viscosity by adding liquid plasticizers within a range that does not affect other properties such as curability. Further, the viscosity can be lowered by raising the temperature of the photosensitive resin composition at the time of use, but since it may change in quality depending on the temperature, it is necessary to use in a temperature range where such a phenomenon does not occur.

On the other hand, in order to increase the viscosity of the composition, a high molecular weight component such as unsaturated polyurethane or unsaturated polyester is added, or an ethylenic unsaturated compound having a functional group capable of reacting with an epoxy group, or ethylene. It is also effective to use a compound having a large molecular weight as the ethylenically unsaturated compound having two or more polyunsaturated bonds. In order to cure the photosensitive resin composition of the present invention, it is not necessary to add a compound that generates a free radical by irradiation with high energy rays, but such a compound is used as an ultraviolet absorber for the purpose of adjusting sensitivity characteristics. You can use it.

The photosensitive resin composition of the present invention may be mixed with a filler. Examples of the filler to be mixed include pigment, carbon black, organic fine particles, ceramic fine particles, and metal powder. The filler that can be used in the present invention is not particularly limited, but titanium oxide, calcium carbonate, magnesium carbonate, silica, metal oxides such as alumina, talc, chromate, ferrocyanide, various metal sulfates, Inorganic pigments such as sulfides, selenides, phosphates, phthalocyanines, quinacridones,
Isoindolinone-based, perinone-based, dioxazine-based organic pigments, carbon black, or gold,
Silver, copper, platinum, palladium, nickel, aluminum,
Examples thereof include a metal simple substance such as silicon and brass, an alloy powder, a metal powder whose surface is coated with a different metal, a colored filler in which a pigment or a dye is dispersed in fine particles formed of an organic compound, and the like. The number average particle diameter of the powder or particles used as the filler of the present invention is 0.0
1 μm or more and 100 μm or less, preferably 0.1 μm or more and 30 μm or less, more preferably 0.3 μm or more and 10 μm
The following are desirable: If it is larger than 100 μm, it becomes difficult to fill the minute gaps and it becomes difficult to apply it in a thin film form. If it is less than 0.01 μm, the viscosity of the photosensitive resin composition increases, making it difficult to fill the minute gaps, and handling becomes difficult due to thixotropy and the like.

Further, when the particle size distribution is wide, the packing factor becomes high when the filler is contained in a high concentration, so that the permeability of actinic rays is lowered. The shape of the filler used in the present invention is not particularly limited, and may be any shape such as spherical, flat, or polyhedral. Further, it may be a porous particle, a particle having a hollow inside such as a microcapsule, or a fine particle having a layered structure such as clay mineral or mica, in which different molecules are intercalated between layers.

The content of the filler that can be used in the present invention is preferably 40 parts by weight or less based on 100 parts by weight of the photosensitive resin composition containing the compounds (A) to (C).
It is more preferably 30 parts by weight or less, still more preferably 20 parts by weight or less. When the amount is more than 40 parts by weight, the actinic ray is difficult to penetrate to the inside, and the curability of the obtained cured product is likely to be insufficient, and the viscosity of the photosensitive resin composition is increased to fill the minute gaps. Becomes difficult.

Further, the adhesiveness can be further improved by incorporating the above organic fine particles, particularly fine particles having a hydroxyl group such as cellulose fine particles. Further, by incorporating fine ceramic particles such as boron nitride, silicon nitride, silicon carbide and titanium nitride, the durability can be improved. For the purpose of improving the light transmittance of the photosensitive resin composition containing the filler of the present invention, the refractive index of the filler mixed with the photosensitive resin composition, the refractive index of the photosensitive resin composition having no filler It is desirable to match the rate. The range of the refractive index of the filler is 0.8 to 1.5 times, preferably 0.95 to 1.1 times the refractive index of the photosensitive resin composition having no filler. It is also effective to select a filler having a particle size smaller than the wavelength of the transmitted light. Examples thereof include inorganic nanoparticles such as colloidal metal and silica, and organic ultrafine particles such as latex particles made of a butadiene / styrene copolymer.

Further, a dye or pigment may be added for the purpose of adjusting the light transmittance. Examples thereof include dyes such as azo dyes, anthraquinone dyes, indigoid dyes, triphenylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes and cyanine dyes. Further, in the photosensitive resin composition used in the present invention,
Additives may be added for the purpose of improving the adhesion to the substrate on which the photosensitive resin composition is placed, the antistatic property, the dispersibility of the filler, and the like. Further, a small amount of a polymerization inhibitor may be added for the purpose of extending the pot life of the photosensitive resin composition.

In the photosensitive resin composition used in the present invention, it is possible to add an acid / base trapping agent for trapping an acid or a base generated upon irradiation with actinic rays. In the present invention, it is preferable to add the trapping agent also from the viewpoint of controlling the curing reaction. It is also effective in applications where the acid or base does not remain in the finally cured product. As a method for producing the photosensitive resin composition used in the present invention, an ordinary kneading method can be used. However, in the case of mixing insoluble powders and particles, a method of mechanically stirring, a method of using a three-roll kneading device for mixing while applying a shearing force, and the like can be mentioned. In particular, for applications in which the colorant needs to be uniformly dispersed in the photosensitive resin composition, a method of mixing using a kneading device such as a triple roll is effective.

A method of coating the surface of the substrate with the photosensitive resin composition according to the present invention will be described. The photosensitive resin composition described above is applied to the surface of a base material and used. For example, a spin coating method, a spray coating method, a roll coating method or the like can be applied. The spin coating method is preferable for controlling the film thickness in the thin film state, and the roll coating method and the spray coating method are preferable as the method for controlling the film thickness in the thick film state. As the high energy ray of the present invention, one that emits ultraviolet rays having a wavelength of 300 to 400 nm is preferable, and an ultraviolet fluorescent lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, or an electron beam, an ion beam, a laser, or the like. The high-energy rays, etc., which are usually used for curing the photosensitive resin composition can be used.

The present invention will be described in more detail with reference to the following examples. The present invention is not limited to the examples below.

[0060]

EXAMPLE 1 (1) 3,4-Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate (manufactured by Union Carbide: trademark "UVR-61"
10 ") 71 parts by weight, (3) 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: trademark" light acrylate 1,9ND-A ") 5 parts by weight, (2) polypropylene glycol monomethacrylate (NOF Corporation) Made: Trademark "Blenmer PP-1000", average molecular weight 1014)
24 parts by weight, (C) Triarylsulfonium hexafluorophosphate mixture propylene carbonate 50% by weight solution (manufactured by Union Carbide: trademark "UVI-69"
90 ") and 4 parts by weight and 2.0 parts by weight of a trademark" BYK-UV3500 "(manufactured by BYK Japan KK: polydimethylsiloxane having a polyether modified acrylic group) were mixed to obtain a liquid photosensitive resin composition a. .

20 ° C. of the obtained liquid photosensitive resin composition a
As a result of measuring the viscosity at 1 using a B-type viscometer, 1
It was 38 mPa · s. The surface tension of the obtained liquid photosensitive resin composition a was measured by a surface tensiometer "CBV" at 25 ° C.
P-Z "(trademark, manufactured by Kyowa Interface Science Co., Ltd.),
It was 42 mN / m.

An example of a method for forming an adhesive three-dimensional pattern will be described with reference to FIG. First, the uncured photosensitive resin composition a was applied to a film thickness of 20 μm on a silicon wafer whose surface was heat-treated by a spin coating method.
FIG. 1A shows this state. Next, the entire surface of the uncured adhesive layer made of the photosensitive resin composition a applied was irradiated with 500 mJ / cm ² of light from a 3 kW high pressure mercury lamp in air to form a semi-cured state. 1800 mJ to completely cure
/ Cm ^2, which is less than 30% of the amount of energy required for complete curing. FIG. 1B shows this state (the arrow in the figure indicates a high energy ray).
Next, the third harmonic of the YAG laser (wavelength: 355n
The beam of m) was scanned by moving the galvanometer mirror, and the unnecessary portion of the semi-cured adhesive was ablated and removed to obtain a three-dimensional pattern having adhesiveness.
FIG. 1C shows this state. The minimum dimension of the three-dimensional pattern was 30 μm. The Shore D hardness (0 second) of the three-dimensional pattern in the semi-cured state was 30 degrees. Further, the hardness of the three-dimensional structure which was finally cured by irradiation with light from a high pressure mercury lamp up to 2000 mJ / cm ² was 82 degrees.
The laser processing machine used for processing the three-dimensional pattern was a trademark "LAVIA-UV2000" manufactured by Sumitomo Heavy Industries, Ltd. As a result of tacking the surface of the three-dimensional pattern in the semi-cured state using a tack tester manufactured by Toyo Seiki Seisaku-sho, the result was 588 N / m.

Next, a quartz glass substrate having a thickness of 1 mm was placed on the adhesive three-dimensional pattern formed on the silicon wafer, and the quartz glass substrate was temporarily fixed by pressure bonding. FIG. 1D shows this state. Furthermore, the light of a 3 kW high pressure mercury lamp was radiated through the temporarily fixed quartz glass to completely cure the three-dimensional pattern in the semi-cured state. FIG. 1 (e) shows this state. It was not possible to peel off the structure formed by adhering the silicon wafer and the quartz glass by the cured three-dimensional pattern. Further, using a dicing saw, the structure is 10 mm × 1.
Even when cut to a size of 0 mm, the silicon wafer and the quartz glass could not be peeled off.

Further, as a result of observing the cut surface with a dicing saw with a microscope, no voids were observed at the interface between the silicon wafer and the adhesive and at the interface between the adhesive and the quartz glass substrate. Separately, the physical properties of the final cured product were evaluated. A dumbbell-shaped test piece with a thickness of 1 mm, an effective length of 30 mm and a width of 3 mm was irradiated with light from a high pressure mercury lamp at 3000 mJ / cm ^2.
It was irradiated and cured to prepare. Shore D hardness (0 seconds) is 8
It was 2 degrees, the tensile test strength was 14.1 MPa, and the elongation rate was 59%.

[0065]

Example 2 (1) 3,4-Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate (manufactured by Union Carbide: trademark "UVR-61"
10 ") 71 parts by weight, (3) 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: trademark" light acrylate 1,9ND-A ") 20 parts by weight, (2) polypropylene glycol monomethacrylate (NOF Corporation) Product: Trademark "Blenmer PP-1000", average molecular weight 101
4) 9 parts by weight, (C) triarylsulfonium hexafluorophosphate mixture propylene carbonate 50% by weight solution (manufactured by Union Carbide: trademark "UVI-6"
990 ") 4 parts by weight, trademark" BYK-UV3510 "
A liquid photosensitive resin composition b was obtained by mixing 0.6 parts by weight of (polyether-modified polydimethylsiloxane manufactured by BYK Japan KK).

20 ° C. of the obtained liquid photosensitive resin composition b
As a result of measuring the viscosity at 8 using a B-type viscometer,
It was 0 mPa · s. The surface tension of the obtained liquid photosensitive resin composition b was measured by a surface tensiometer “CBVP at 25 ° C.
-Z "(trademark, manufactured by Kyowa Interface Science Co., Ltd.), 2
It was 2 mN / m. In the same manner as in Example 1, a three-dimensional pattern having adhesiveness and then a quartz glass substrate having a thickness of 1 mm were adhered, and the three-dimensional pattern was finally cured to form a structure.

The tack of the surface of the three-dimensional pattern in the semi-cured state was 637 N / m. The Shore D hardness (0 second) of the three-dimensional pattern in the semi-cured state was 30 degrees.
Furthermore, the hardness of the three-dimensional pattern which was finally cured by irradiating the light of the high pressure mercury lamp up to 2000 mJ / cm ² was 75.
It was degree. In addition, a silicon wafer with adhesive 3
The quartz glass substrate could not be peeled off from the silicon wafer in the structure adhered and cured to the quartz glass substrate via the three-dimensional pattern. Further, as in Example 1, a dicing saw was used to cut into a size of 10 mm × 10 mm, and the cross section was observed. As a result, voids and the like were observed at the interface between the silicon wafer and the adhesive and the interface between the adhesive and the quartz glass substrate. Was not done.

Separately, the physical properties of the final cured product were evaluated. A dumbbell-shaped test piece having a thickness of 1 mm, an effective length of 30 mm, and a width of 3 mm was irradiated with 2000 mJ / cm ² of light from a high-pressure mercury lamp and cured. Shore D hardness (0 seconds) is 75 degrees, tensile test strength is 17.2 MPa, elongation is 2
It was 0%.

[0069]

Example 3 (1) 71 parts by weight of bis- (3,4-epoxycyclohexyl) adipate (trade name "UVR-6128" manufactured by Union Carbide), (3) 1,9-nonanediol diacrylate (Kyoeisha Chemical Co., Ltd.) Made: trademark "light acrylate 1,9ND-A") 20 parts by weight,
(2) 9 parts by weight of polypropylene glycol monomethacrylate (trade name "Blenmer PP-1000, average molecular weight 1014" manufactured by NOF CORPORATION), (C) Triarylsulfonium hexafluorophosphate mixture propylene carbonate 50% by weight solution (Union Carbide Company:
Trademark "UVI-6990") 4 parts by weight, Trademark "BYK-
356 "(manufactured by Big Chemie Japan Co., Ltd .: acrylic-based polymer) (0.7 parts by weight) is mixed to obtain a liquid photosensitive resin composition c.
Got

20 ° C. of the obtained liquid photosensitive resin composition c
As a result of measuring the viscosity at 8 using a B-type viscometer,
It was 0 mPa · s. The surface tension of the obtained liquid photosensitive resin composition c at 25 ° C. was measured by a surface tensiometer “CBVP”.
-Z "(trademark, manufactured by Kyowa Interface Science Co., Ltd.), 3
It was 4 mN / m. In the same manner as in Example 1, a three-dimensional pattern having adhesiveness and then a quartz glass substrate having a thickness of 1 mm were adhered, and the three-dimensional pattern was finally cured to form a structure.

The tack of the surface of the three-dimensional pattern in the semi-cured state was 539 N / m. The Shore D hardness (0 seconds) of the three-dimensional pattern in the semi-cured state was 20 degrees.
Furthermore, the hardness of the three-dimensional pattern that was finally cured by irradiating the light of a high-pressure mercury lamp up to 2000 mJ / cm ² was 60.
It was degree. In addition, a silicon wafer with adhesive 3
The quartz glass substrate could not be peeled off from the silicon wafer in the structure adhered and cured to the quartz glass substrate via the three-dimensional pattern. Further, as in Example 1, a dicing saw was used to cut into a size of 10 mm × 10 mm, and the cross section was observed. As a result, voids and the like were observed at the interface between the silicon wafer and the adhesive and the interface between the adhesive and the quartz glass substrate. Was not done.

Separately, the physical properties of the final cured product were evaluated. A dumbbell-shaped test piece having a thickness of 1 mm, an effective length of 30 mm, and a width of 3 mm was irradiated with 2000 mJ / cm ² of light from a high-pressure mercury lamp and cured. Shore D hardness (0 seconds) is 60 degrees, tensile test strength is 18.3 MPa, elongation is 5
It was 7%.

[0073]

Example 4 (1) 3,4-Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate (manufactured by Union Carbide: trademark "UVR-61"
10 ") 35.5 parts by weight, and xylylene dioxetane (trade name" OXT-121 "manufactured by Toagosei Co., Ltd.) 35.5.
Parts by weight, (3) 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: trademark "light acrylate 1,9N"
D-A ") 20 parts by weight, (2) polypropylene glycol monomethacrylate (manufactured by NOF CORPORATION: trademark" Blenmer PP-1000 ", average molecular weight 1014) 9 parts by weight,
(C) Triarylsulfonium hexafluorophosphate mixture 50% by weight solution of propylene carbonate (manufactured by Union Carbide: trademark "UVI-6990") 4 parts by weight, trademark "BYK-UV3510" (Big Chemie
A liquid photosensitive resin composition d was obtained by mixing 0.6 part by weight of Japan-made: polyether-modified polydimethylsiloxane).

20 ° C. of the obtained liquid photosensitive resin composition d
As a result of measuring the viscosity at 1 using a B-type viscometer, 1
It was 15 mPa · s. The surface tension of the obtained liquid photosensitive resin composition d was measured by a surface tensiometer "CBV" at 25 ° C.
P-Z "(trademark, manufactured by Kyowa Interface Science Co., Ltd.),
It was 21 mN / m. In the same manner as in Example 1, a three-dimensional pattern having adhesiveness and then a quartz glass substrate having a thickness of 1 mm were adhered, and the three-dimensional pattern was finally cured to form a structure.

The tack of the surface of the three-dimensional pattern in the semi-cured state was 490 N / m. The Shore D hardness (0 second) of the three-dimensional pattern in the semi-cured state was 30 degrees.
Furthermore, the hardness of the three-dimensional pattern which was finally cured by irradiating the light of the high pressure mercury lamp up to 2000 mJ / cm ² was 86.
It was degree. In addition, a silicon wafer with adhesive 3
The quartz glass substrate could not be peeled off from the silicon wafer in the structure adhered and cured to the quartz glass substrate via the three-dimensional pattern. Further, as in Example 1, a dicing saw was used to cut into a size of 10 mm × 10 mm, and the cross section was observed. As a result, voids and the like were observed at the interface between the silicon wafer and the adhesive and the interface between the adhesive and the quartz glass substrate. Was not done.

Separately, the physical properties of the final cured product were evaluated. A dumbbell-shaped test piece having a thickness of 1 mm, an effective length of 30 mm, and a width of 3 mm was irradiated with 2000 mJ / cm ² of light from a high-pressure mercury lamp and cured. Shore D hardness (0 seconds) is 86 degrees, tensile test strength is 33.2 MPa, elongation is
It was 12%.

[0077]

Example 5 (1) 3,4-Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate (manufactured by Union Carbide: trademark "UVR-61"
10 ") 71 parts by weight, (3) 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: trademark" light acrylate 1,9ND-A ") 5 parts by weight, (2) 2-hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd.)" Company: Trademark "light ester HO", molecular weight 130) 24 parts by weight, (C)
A liquid photosensitive resin composition e was obtained by mixing 4 parts by weight of a 50% by weight triarylsulfonium hexafluorophosphate mixture propylene carbonate solution (trade name "UVI-6990" manufactured by Union Carbide Co.).

20 ° C. of the obtained liquid photosensitive resin composition e
The viscosity at 6 was measured using a B-type viscometer.
It was 5 mPa · s. The surface tension of the obtained liquid photosensitive resin composition e at 25 ° C. was measured by a surface tensiometer “CBVP”.
-Z "(trademark, manufactured by Kyowa Interface Science Co., Ltd.), 4
It was 5 mN / m. In the same manner as in Example 1, a three-dimensional pattern having adhesiveness and then a quartz glass substrate having a thickness of 1 mm were adhered, and the three-dimensional pattern was finally cured to form a structure.

The tack of the surface of the three-dimensional pattern in the semi-cured state was 441 N / m. The Shore D hardness (0 seconds) of the semi-cured three-dimensional structure was 30 degrees. Further, the hardness of the three-dimensional structure which was finally cured by irradiation with light from a high pressure mercury lamp to a total of 2000 mJ / cm ² was 85 degrees. Further, in a structure in which a silicon wafer is adhesively cured on a quartz glass substrate via an adhesive three-dimensional pattern, the quartz glass substrate could not be peeled off from the silicon wafer. Further, as in Example 1, a dicing saw was used to cut into a size of 10 mm × 10 mm, and the cross section was observed. As a result, voids and the like were observed at the interface between the silicon wafer and the adhesive and the interface between the adhesive and the quartz glass substrate. Was not done.

Separately, the physical properties of the final cured product were evaluated. A dumbbell-shaped test piece having a thickness of 1 mm, an effective length of 30 mm, and a width of 3 mm was irradiated with 2000 mJ / cm ² of light from a high-pressure mercury lamp and cured. Shore D hardness (0 seconds) is 85 degrees, tensile test strength is 44.1 MPa, elongation is
It was 8%.

[0081]

EXAMPLE 6 (1) 3,4-Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate (manufactured by Union Carbide: trademark "UVR-61"
10 ") 71 parts by weight, (2) 2-hydroxyethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: trademark" light ester H "
O ", molecular weight 130) 29 parts by weight, (C) triarylsulfonium hexafluorophosphate mixture propylene carbonate 50% by weight solution (trade name" UVI-6990 "manufactured by Union Carbide Co., Ltd.) 4 parts by weight are mixed to obtain a liquid photosensitive material. Resin composition f was obtained.

20 ° C. of the obtained liquid photosensitive resin composition f
As a result of measuring the viscosity at 5 using a B-type viscometer, 5
It was 9 mPa · s. The surface tension of the obtained liquid photosensitive resin composition f was measured by a surface tensiometer “CBVP” at 25 ° C.
-Z "(trademark, manufactured by Kyowa Interface Science Co., Ltd.), 4
It was 7 mN / m. In the same manner as in Example 1, a three-dimensional pattern having adhesiveness and then a quartz glass substrate having a thickness of 1 mm were adhered, and the three-dimensional pattern was finally cured to form a structure.

The tack of the surface of the three-dimensional pattern in the semi-cured state was 568 N / m. The Shore D hardness (0 second) of the three-dimensional pattern in the semi-cured state was 30 degrees.
Furthermore, the hardness of the three-dimensional pattern that was finally cured by irradiating the light of the high pressure mercury lamp up to 2000 mJ / cm ² is 90.
It was degree. In addition, a silicon wafer with adhesive 3
The quartz glass substrate could not be peeled off from the silicon wafer in the structure adhered and cured to the quartz glass substrate via the three-dimensional pattern. Further, as in Example 1, a dicing saw was used to cut into a size of 10 mm × 10 mm, and the cross section was observed. As a result, voids and the like were observed at the interface between the silicon wafer and the adhesive and the interface between the adhesive and the quartz glass substrate. Was not done.

Separately, the physical properties of the final cured product were evaluated. A dumbbell-shaped test piece having a thickness of 1 mm, an effective length of 30 mm, and a width of 3 mm was irradiated with 2000 mJ / cm ² of light from a high-pressure mercury lamp and cured. Shore D hardness (0 seconds) is 90 degrees, tensile test strength is 48.0 MPa, elongation is
It was 4%.

[0085]

Example 7 A liquid photosensitive resin composition a was prepared in the same manner as in Example 1. 5 parts by weight of spherical silica particles having an average particle diameter of 3 μm were mixed with 100 parts by weight of this photosensitive resin composition a to obtain a photosensitive resin composition g. In the same manner as in Example 1, a three-dimensional pattern having adhesiveness and then
A quartz glass substrate having a thickness of 1 mm was adhered and the three-dimensional pattern was finally cured to form a structure.

The tack of the surface of the three-dimensional pattern in the semi-cured state was 539 N / m. The Shore D hardness (0 second) of the three-dimensional pattern in the semi-cured state was 30 degrees.
Furthermore, the hardness of the three-dimensional pattern that was finally cured by irradiating the light of the high pressure mercury lamp up to 2000 mJ / cm ² is 90.
It was degree. In addition, a silicon wafer with adhesive 3
The quartz glass substrate could not be peeled off from the silicon wafer in the structure adhered and cured to the quartz glass substrate via the three-dimensional structure. Further, as in Example 1, a dicing saw was used to cut into a size of 10 mm × 10 mm, and the cross section was observed. As a result, voids and the like were observed at the interface between the silicon wafer and the adhesive and the interface between the adhesive and the quartz glass substrate. Was not done.

[0087]

Example 8 (1) 3,4-Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate (manufactured by Union Carbide: trademark "UVR-61"
10 ") 71 parts by weight, (3) 3 parts by weight of a urethane diacrylate compound (trade name:" AH-600 "manufactured by Kyoeisha Chemical Co., Ltd.) obtained by reacting 2-hydroxy-3-phenoxy acrylate and hexamethylene diisocyanate,
(2) Polypropylene glycol monomethacrylate (made by NOF CORPORATION: trademark "Blenmer PP-1000",
Average molecular weight 1014) 26 parts by weight, (C) triarylsulfonium hexafluorophosphate mixture propylene carbonate 50% by weight solution (manufactured by Union Carbide: trademark "UVI-6990") 4 parts by weight, trademark "BY"
Liquid photosensitive resin composition h by mixing 2.0 parts by weight of K-UV3500 "(manufactured by BYK Japan KK: polydimethylsiloxane having a polyether modified acrylic group)
Got

20 ° C. of the obtained liquid photosensitive resin composition h
As a result of measuring the viscosity at 8 using a B-type viscometer,
It was 0 mPa · s. In the same manner as in Example 1, a three-dimensional pattern having adhesiveness and then a quartz glass substrate having a thickness of 1 mm were adhered, and the three-dimensional pattern was finally cured to form a structure. The tack of the surface of the three-dimensional pattern in the semi-cured state was 529 N / m. The Shore D hardness (0 second) of the three-dimensional pattern in the semi-cured state was 30 degrees. Furthermore, the total pressure of the high pressure mercury lamp is 2000 mJ /
The hardness of the three-dimensional pattern that was finally cured by irradiation up to cm ² was 80 degrees.

Further, a silicon wafer is used as an adhesive 3
The quartz glass substrate could not be peeled off from the silicon wafer in the structure adhered and cured to the quartz glass substrate via the three-dimensional pattern. Further, as in Example 1, a dicing saw was used to cut into a size of 10 mm × 10 mm, and the cross section was observed. As a result, voids and the like were observed at the interface between the silicon wafer and the adhesive and the interface between the adhesive and the quartz glass substrate. Was not done.

[0090]

Example 9 A liquid photosensitive resin composition a was prepared in the same manner as in Example 1. A liquid photosensitive resin compound a ′ was obtained by adding 0.1 part by weight of a light transmittance adjusting dye (trade name “OPLAS Yellow 140” manufactured by Orient Chemical Co., Ltd.) to 100 parts by weight of the liquid photosensitive resin a.

Next, an example of the second method for forming a three-dimensional structure having adhesiveness will be described with reference to FIG. First, an uncured liquid photosensitive resin composition a ′ is applied onto a silicon wafer by a spin coating method so as to have a film thickness of 20 μm. FIG. 2A shows this state. Subsequently, using a projection exposure machine, "UX-4040SC" (trademark, manufactured by Ushio Inc.), light of 1 kW ultra-high pressure mercury lamp was photocured from the liquid photosensitive resin composition a'through a glass photomask. The adhesive layer was irradiated. Figure 2
(B) shows this state (the arrow in the figure indicates the light of the extra-high pressure mercury lamp). The projection exposure machine is an exposure machine that can perform an exposure operation without bringing a photomask into contact with a substrate to be irradiated with light, and because the parallelism of light rays emitted from a projection lens in the exposure machine is high, It enables the formation of fine patterns. The energy amount of the irradiated light was 800 mJ / cm ² . Next, the liquid resin in the uncured portion which was not irradiated with light was blown off with compressed air of 0.5 MPa to be removed. FIG. 2C shows this state. After this, in the same manner as in Example 1, the thickness is 1 mm.
A quartz glass substrate of No. 1 was adhered and cured on the obtained three-dimensional pattern to produce a structure. FIG. 2D shows this state.

The minimum dimension of the adhesive three-dimensional pattern obtained was 20 μm. The tack of the surface of this three-dimensional pattern was 578 N / m. In addition, in a structure in which a silicon wafer is adhesively cured on a quartz glass substrate through an adhesive three-dimensional pattern,
The quartz glass substrate could not be peeled off from the silicon wafer. Further, as in Example 1, a dicing saw was used to cut into a size of 10 mm × 10 mm, and the cross section was observed. As a result, voids and the like were observed at the interface between the silicon wafer and the adhesive and the interface between the adhesive and the quartz glass substrate. Was not done.

[0093]

Example 10 In the same manner as in Example 4, a liquid photosensitive resin composition d was prepared. A liquid photosensitive resin compound d ′ was obtained by adding 0.1 part by weight of a light transmittance adjusting dye (trade name “OPLAS Yellow 140” manufactured by Orient Chemical Co., Ltd.) to 100 parts by weight of the liquid photosensitive resin d. In the same manner as in Example 9, the three-dimensional pattern having adhesiveness and then,
A quartz glass substrate having a thickness of 1 mm was adhered and the three-dimensional pattern was finally cured to form a structure.

The tack of the surface of the three-dimensional pattern in the semi-cured state was 510 N / m. Further, in a structure in which a silicon wafer is adhesively cured on a quartz glass substrate via an adhesive three-dimensional pattern, the quartz glass substrate could not be peeled off from the silicon wafer. Further, using a dicing saw as in Example 1,
As a result of observing the cross section after cutting to a size of 0 mm × 10 mm, no voids were observed at the interface between the silicon wafer and the adhesive and the interface between the adhesive and the quartz glass substrate.

[0095]

Comparative Example 1 In the same manner as in Example 9, a liquid photosensitive resin composition a ′ was prepared. Next, a semi-cured cured product was formed in the light-irradiated portion by the same method as in Example 9 until the step of exposing using a projection exposure machine.
Then, at room temperature (25 ° C.) using N-methylpyrrolidone, which is an organic solvent capable of dissolving the liquid photosensitive resin composition a.
The uncured part was developed in. As a result, even the semi-cured part was completely removed.

[0096]

[Comparative Example 2] 50 parts by weight of unsaturated polyester resin having a number average molecular weight of 2000 and 50 parts by weight of tripropylene glycol diacrylate (trade name "M-220" manufactured by Toagosei Co., Ltd.) as a bifunctional acrylate compound and initiation of photoradical polymerization. 4 parts by weight of benzyl dimethyl ketal (trade name "Irgacure 651" manufactured by Ciba-Geigy Co., Ltd.) as an agent, and a dye for adjusting light transmittance (trade name "OPLAS manufactured by Orient Chemical Co., Ltd."
Yellow 140 ″) 0.1 parts by weight was mixed to obtain a liquid photosensitive resin composition j. The unsaturated polyester resin was synthesized by dehydration-condensing 0.3 of fumaric acid, 0.5 of adipic acid and 0.2 of itaconic acid with respect to 1 of diethylene glycol.

20 ° C. of the obtained liquid photosensitive resin composition j
As a result of measuring the viscosity at 5 using a B-type viscometer, 5
It was 500 mPa · s. As in Example 9, 3
A dimensional pattern was formed. However, an attempt was made to remove the uncured portion using compressed air, but the removal was only half of the film thickness and could not be completely removed. Also,
The surface of the cured product was tacky, and the tack was measured and found to be 294 N / m.

In the same manner as in Example 1, a quartz glass substrate having a thickness of 1 mm was placed on the obtained three-dimensional pattern, pressure-bonded and temporarily fixed, and then, through the quartz glass, light of a 3 kW high-pressure mercury lamp was irradiated to semi-cure. The three-dimensional pattern of conditions was completely cured. However, the quartz glass substrate could be easily peeled off from the silicon wafer by hand.

[0099]

EFFECTS OF THE INVENTION According to the present invention, a fine pattern can be formed, the adhesiveness is maintained after the pattern is formed, and thereafter, another substrate is used in the process of final curing by irradiation with high energy rays or heating. Can be glued,
The final cured product can provide a three-dimensional pattern having good physical properties and adhesiveness useful for electronic materials and the like.

[Brief description of drawings]

FIG. 1 is a cross-sectional view illustrating an example of a first method of forming an adhesive three-dimensional pattern of the present invention.

FIG. 2 is a sectional view illustrating an example of a second method of forming a three-dimensional pattern having adhesiveness of the present invention.

[Explanation of symbols]

1 Silicon wafer 2 Uncured photosensitive resin layer 3 Semi-cured photosensitive resin layer 4 Space removed by laser 5 Quartz glass substrate 6 Finally cured photosensitive resin layer 7 Glass photomask 8 Light shield 9 Space formed by removing uncured resin

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H025 AA13 AA14 AB17 AB20 AC01                       AD01 BC13 BC42 BC86 BD03                       BD23 BE00 FA19 FA30 FA39                 4J005 AA07 BB01                 4J036 AB01 AB02 AB10 AD08 AJ09                       AJ10 AK19 EA01 EA02 EA04                       EA09 FA02 FB10 GA22 GA24                       GA25 HA02 JA09

Claims (8)

[Claims] 1. A semi-cured photosensitive resin comprising (A) a compound having a ring-opening polymerizable reactive group in the molecule and (C) a compound capable of absorbing a high energy ray to generate an acid or a base. A three-dimensional pattern composed of a composition, wherein the pattern has a minimum dimension of 50 μm or less and a height of 1 μm.
A three-dimensional pattern having an adhesiveness of not less than m and not more than 1 mm, and the tack of the surface of the three-dimensional pattern is not less than 98 N / m. 2. A liquid photosensitive material comprising, on a substrate, (A) a compound having a ring-opening polymerizable reactive group in the molecule and (C) a compound capable of absorbing a high energy ray to generate an acid or a base, as essential components. Characterized in that a semi-cured state is formed by irradiating a high-energy ray on the entire surface of the functional resin composition layer, and then a part of the semi-cured adhesive layer is removed by a laser to form a pattern. A method for forming a three-dimensional pattern having adhesiveness. 3. A liquid photosensitive material comprising, on a substrate, (A) a compound having a ring-opening polymerizable reactive group in the molecule and (C) a compound capable of absorbing a high energy ray to generate an acid or a base, as essential components. Of a photosensitive resin composition layer and irradiating a part of it with a high energy beam to make it a semi-cured state, and then removing the liquid photosensitive resin composition in the unirradiated portion of the high energy beam to form a pattern. A method for forming a three-dimensional pattern having adhesiveness, which comprises: 4. A photosensitive resin composition comprising (A) a compound having a ring-opening polymerizable reactive group in the molecule and (C) a compound capable of absorbing a high energy ray and generating an acid or a base, as essential components. A photosensitive resin composition for three-dimensional pattern formation having adhesiveness, which has a viscosity at 20 ° C. of 1 mPa · s or more and 5000 mPa · s or less. 5. (B) further comprising (B) an ethylenically unsaturated compound having an ethylenically unsaturated bond in the molecule,
The component is 2 to 200 parts by weight based on 100 parts by weight of the component (A), and the component (C) is contained in an amount of 0.1 to 10 wt% based on the total weight of the components (A) and (B). A photosensitive resin composition for forming a three-dimensional pattern having adhesiveness. 6. The component (A) is a compound having in the molecule thereof (1) one or more ring-opening polymerizable reactive groups selected from an epoxy group or an oxetane group, and the component (B) is
To 100 parts by weight of component (A), 1 to 100 parts by weight of (2) an ethylenically unsaturated compound having a hydroxyl group and an ethylenically unsaturated bond in the molecule at the same time, and (3) ethylene having no hydroxyl group in the molecule 6. 1 to 100 parts by weight of an ethylenically unsaturated compound having two or more polyunsaturated bonds.
A photosensitive resin composition for three-dimensional pattern formation, which has the adhesiveness described above. 7. A cured product obtained by irradiating the three-dimensional pattern having adhesiveness according to claim 1 with a high energy ray or applying heat. 8. The three-dimensional pattern having adhesiveness according to claim 1, wherein another base material is placed on the three-dimensional pattern, and is applied by being irradiated with high energy rays or heated to form a bond. The structure to do.