TW322469B - Vinyl ether compounds having additional functional groups other than vinyl ether groups and the use in the formulation of curable compositions - Google Patents

Abstract

Vinyl ether compounds having additional functional groups other than vinyl ether groups and the use in the formulation of curable compositions which have at least one vinyl ether group which also contain in the molecule at least one further functional group selected from acrylate, methacrylate, epoxy, alkenyl, cycloalkenyl and vinylaryl groups, to compositions especially for stereolithography,comprising those vinyl ether compounds and to a method of producing three-dimensional objects using those compositions.

Description

322469 A7 B7_ V. Description of the invention (/) The present invention relates to a novel vinyl ether compound, its application, the composition containing these compounds, and the application of these compositions in the manufacture of hardened products, especially the method of stereolithography Application for manufacturing hardened products. As early as κ, it has been known to use a compound with a carbon-carbon double bond as the polymerizable component of the hardenable compound, which also includes a polyvinyl ether compound. In special cases, the hardening of the polymerizable composition may be carried out in a stepwise manner in the desired manner. For example, WO 92/200 14 describes a polymerizable composition which includes an epoxy compound as another polymerizable component in addition to a vinyl ether compound. The use of this composition makes it possible to produce a three-dimensional lithography molding that is particularly loyal to the mold. However, the composition described in K also has its disadvantages. For example, its light sensitivity is poor. Furthermore, the mechanical properties of materials made using this composition, especially the elastic modulus (E modulus) and tear elongation, are often unsatisfactory. The present invention aims to propose ways to improve the properties of the composition in question. Surprisingly, I found that the use of vinyl compounds as polymerizable ingredients may also result in a photohardenable composition, which is very sensitive to light, in addition to being able to produce a fully hardened state with high network density and high Uniform material with elastic modulus, if it is an intramolecular vinyl ether compound, it has better tear resistance. In addition to vinyl ether, functional groups that are not vinyl ether can undergo cross-linking reaction, such as acrylate, methyl alcohol Acrylate, epoxy, alkenyl, especially vinylalkyl, cycloalkenyl and vinylaryl, especially styryl. The present invention therefore relates to a compound containing at least one vinyl ether, which is divided into -3-This paper scale is applicable to the Chinese National Standard (CNS) A4 present grid (210X297mm) binding and thread (please read the precautions on the back first (Fill in this page) 322469 A7 B7 5. Description of the invention (The sub-group also contains at least another functional group selected from acrylate, methacrylate, epoxy, alkenyl, cycloalkenyl and vinyl aryl groups. The present invention The preferred molecular weight of vinyl ether is less than 30,000, and it is preferably flowable at room temperature, in other words, it is flowable below about 10 to 30 * 0. Examples of preferred vinyl ether compounds of the present invention are The compound of the formula h2c = ch-ol · -A, where the symbols used in the formula and the following formula are defined as follows: A is a Z valence group selected from the following formula (1), (2), (3) and (4)-( CxH2x) -〇, (1) ⑵ ch2 R2〇 /, CH2- (-(CxH2x) -0 r2o

o II (3) —— (CsH2s) — O-C — [D]-R1

o II CO-(Csh2s) CH '1 Binding II line I (please read the precautions on the back before filling in this page) 2-1 2-z The paper size is applicable to the Chinese National Standard (CMS) A4 specification (210X297mm ) 322469 A7 B7 V. Description of the invention (II • (CsH2s) -〇-C- (CtH2t) -7-(CsH2s) -〇-C- (CtH2t) Ο

D] is the following formula Ο / \ ⑶ One (CxH2x) — CH- < CuH2u) — CH ~ CHtv (CyH2y> [E] is 〇1 monoalkylene or C2- alkylene R ° is a hydrogen atom or M1; R1 is a z-valent group selected from aliphatic, cycloaliphatic, aryl, and aliphatic-cycloaliphatic and polyoxyalkylene groups. R2 is a mono-fatty-aromatic I binding line selected under Μ (please Read the precautions on the back before filling in this page) 0 -ch2-cr ° ~ ch2 _ 〇 私 II 4 u -C-NH— R — NH— c — OR5

Ο II R 4 is the basic paper size selected from Μ. Applicable to China National Standard (CNS) Α4 specification (210Χ297 mm) S22469 A7 B7 5. Description of the invention (/)

* 3; (2-(CyH2y)-; R5 is a group selected from

0 II

0 CHc, II-(CmH2m) -〇-C-CH = CH2,-(CmH2m) -0-CC = CH2 Ο /,-(CmH2m) -CH = CH2,-((^ H ^ JO-CHrCR0 ~ CH2 , O / \ • (CmH2m) -CR0—〇1-((: Lu 2; +1),

CH2 _CH2 〆 〇i20 ’t >, ——— CR ^ CH2ia C \\ CH〇

Rs is a (2 z) -valent organic group, which is used together with each carbon group of the following z-based carbon ek © Sub C and C This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Gutter (Please read first Note on the back and then fill in this page) 322469 V. Description of the invention (t) ο)-2Χ Η X (c ⑹ r2o

• C χΗβΗ, the formula is in the order of the count or the whole seat. The single, 1 original ο ο ο ο other R hydrogen 2211 base sum to to to the formula) 4 are all 0120 under 2- , For the sake of imR u when iR is., The hydrogen ring is fat and fat, the ring is supported by the proto-alkane carbon 2 C 5 is less than J to E. Contains C in the form of 5 base support forming ο ( Please read the precautions on the back before filling in this page) -install-book 2U) Η u (c / \ έ The number of integers ου 2 ου ΙΓ to 4 1 到 为 立 为 独 V V yl Minghewei The number of XZ books is integer ο 2 to 2 is independent. 0 2 or the formula is the compound of A or 2 under the better line type. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 5) Description of invention (⑺ A7 B7 H2C = CH- 0-(CH2)-0,

, CH2I CH R20 ch2-o- • R] and ⑻ H2C = CH- 0-(CH2) -O R20

Among them, R1, R2, R6, parent and 2 are defined as above with other symbols. The exponents i, m, s, t, .u, X and y are advantageously upper limit values 8'i, m, s, t and u are advantageously upper limit values 6 or 4. Preferably, it is a hydrogen atom and R2 is preferably -ch2-chch2. In the compound of the present invention, R 1 is preferably a Z-valent group selected from the following components (a) A fatty group containing 2 to 20 carbon atoms ( b) cycloaliphatic groups and aromatic groups each containing 6 to 14 carbon atoms, (c) fatty-aromatic groups and fatty monocyclic fatty groups each containing 7 to 25 carbon atoms, and (d) the following formula R? — C 0 C SH 2 g〕 η —He Yi (CgHz g)--8- This paper wave scale is applicable to China National Standard (CNS) A4 specification (210X297mm)! III Pack i III Order IIIIII line (please read the back first (Notes to fill out this page)

322469 A1 B7 5. Description of the invention (1) [0 C gH 2 g] n-1 polyoxyalkylene, wherein R7 is an alkyl group containing 1 to 8 carbon atoms, g is 1 to 8 polyoxyalkylene The alkylene unit of the group has an average carbon atom, and η is an integer of 2 to 20. The symbol # s 〃 represents the average number of carbon atoms calculated for the alkylene unit corresponding to the polyoxyalkylene group. Therefore, the s index does not need to be an integer, because the polyoxyalkylene group can be formed at different positions of the number of carbon atoms. In addition, different proportions of monomers can also be used. Examples of possible monomers are ethylene oxide, propylene oxide and tetrahydrofuran. The index g preferably has a value of 2 or 3 or a value between 2 and 3, and thus is a polyether formed by the military position of ethylene oxide and / or propylene oxide. R 1 may not be substituted or may contain one or more substituents. If it is an aliphatic group, R1 is selected from (Ci -C4) alkoxy and halogen substituents; if it is other types, R1 is selected from (Ci _C4) alkyl, (Ci _C4) alkoxy and halogen substituents. R1 is especially selected from the following era R3

III (QH2f + 1)-,-(CfH2f>, CH3- [0-CH-CH2] n-,-(CH-CH ^ -tO-C H-CH2) nr, and phenyl; of which R and R3 It is independently hydrogen atom or methyl group, and this paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) ---- ^ ------, 玎 ------ M- ( (Please fill in this page before filling in this note) 5. V. Description of Invention (p) A7 B7 f is an integer from 2 to 20. η is defined as an integer from 2 to 20, preferably from 2 to the end. The preferred ones are compounds of formula (7), wherein R 1 is selected from the group consisting of

I R3-(CfH2f)-,-(C H-CH2)-[0-C H-CH2] n.r,

And phenyl R 4 is selected from the following formula

h3c ‘CH〇 ch3

Ci ^ C: such as-(CyH2y)-,: H3, for example, one (CH 2) 6 R 5 is selected from the group of the following formula 〇o ch3 II III '(CkH2k) -〇-C-CH = CH2,-(CkH2k) -0-CC = CH2

-(CmD-CHsC% R and R3 are both hydrogen atoms or methyl groups; and k is an integer from 2 to 10, the upper limit of the index m is 10, the above description applies to other symbols. Among the examples of this compound R 1 is selected from the group consisting of alkylene groups with 2 to 4 carbon atoms, phenyl group and the following formula 10. This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) --------- -^ .------ tr ------ 0 (please read the precautions on the back before filling in this page) 5. Description of the invention (Base A7 B7 R 4 is the following formula

And R 5 are selected from the group of the following formula: o och3 II III-(c2h4) -o-c-ch = ch2,-(c2h4) -o-c-c = -CH3-CH = CH2 as

Among the vinyl ether compounds, A is a group of formula (1). In other words, for example, the compound of formula (7) can be prepared by firstly using glycidyl ether 0 Rlf ° " CH2-CH ~ CH2] z and the formula Hz C = CH — 0 (CxCH2x) -oh hydroxyalkyl vinyl ether reacts to form a compound of the formula

H2C = CH- Ο-(CxΗ2χ)-ο ch2- ch- ch2- o r1 OH 1 1-The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) binding line (please read the note on the back first (Fill in this page again) 322469 A7 B7 V. Description of the invention (/ 0) Either convert the hydroxyl group to a glycidyl ether group or further convert the hydroxyl group to the diisocyanate and hydroxyl compound R5 of the formula 〇CN_R4-NCO H reaction or react with these two reactant adducts. A in the compound is a group of formula (2), for example, a compound of formula (8) has at least one cycloalkyl group, which is composed of two carbon atoms cf and .C? H2c = ch-o (cxh2x) -o . 9 )

CfH CPH is formed by the entire R6 group or by the two C? * And C9 carbon atoms of the structural unit of formula (9) and part of the R6 group. It should be understood that "cycloalkyl" includes especially polycycloalkyl groups such as bicycloalkyl groups. The term is also intended to include cycloalkyl consisting of two helically connected rings. Preferably, R6 is an organic group containing 3 to 50, particularly preferably 3 to 30, and more preferably 3 to 20 carbon atoms, and R 2 is a group selected from the group consisting of 0II 4 ——C-NH—R- O 11 5 C-OR, in which the binding line (please read the precautions on the back before filling in this page) R4 is selected from the following formula 12 This paper size is suitable for Chinese national standards (CNS) A4 specification (210X297mm) A7 B7 5. Description of invention (/ f

And (C yH 2 y) ―for example, 0 och3 II III-(CkH2k) -〇-C-CH = CH2,-(CkH2k) -0-C-C = CH2, CH〇-(CmH2m) -CH = CH2, b

k is an integer from 2 to 10, and m is an integer from 1 to 10. In the compound of the present invention, A is a group of formula (2), which includes, for example, Rs in the compound forms a cycloalkyl group containing 5 to 7 ring carbon atoms with the carbon atoms cf and C of the group of formula (9), in particular Is cyclopentyl or cyclohexyl, and z is a compound of the present invention where A is a group of formula (2) and also includes compounds having the structural form of the following, wherein R6 is of formula R8-[G]-R9, where R8- Starting with the carbon atoms d * and C? Of the group of the above formula (9) to form a ring containing 5 to 7 ring carbon atoms, especially a cyclopentyl or cyclohexyl ring, a ring containing 5 to 7 ring carbon atoms may be formed Alkyl condensing; and -1 3- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) binding line (please read the note Ϋ on the back before filling in this page) A7 B7 V. Description of invention ( (I) R9-together with carbon atoms ^ and cf of another group of formula (9), the group of formula (9) is a cycloalkyl group containing 5 to 7 ring carbon atoms, especially cyclopentyl or cyclohexyl * Another cycloalkyl group containing 5 to 7 ring carbon atoms is fused, or is itself a cycloalkyl group containing 5 to 7 ring carbon atoms, especially cyclopentyl or cyclohexyl 'can be added to contain 5 to 7 Ring carbon Atoms are condensed. [G] In the above formula, it is a structural unit selected from a single bond and the following formula groups: 0 II -0-, -CH ^-, -C (CH3) 2-, -CO-CH〗-, Ο ο II II ^ -CH2-0-C- (ChH2h) -C-〇-CH2- and -CHChH ^ -O-h is an integer from 1 to 6, especially 2 to 4. Special examples are compounds of the formula

R10 and Ο ο II II -CHrO-C- (CH2) h-C-0-CH:

Among them, R1 0 and Ri 3, one of which is the formula η2 C =: CH — 0 one (C Η 2) Χ-0-, the other is the formula R2〇_, the same, R 1 1 and R1 2 One of them is H2 C = CH — 〇 一 (C 1-4-This paper size is applicable; National Standard (CNS) A4 specification (210X297mm) ------------ ^ ------. Order ------ ^ (Please read the precautions on the back before filling in the cornel) A7 B7 V. Description of the invention (Μ) Hz) X— 〇—, the other is formula R2 〇_, where X and h are independently integers from 2 to 4. The vinyl ether compound of which A is a group of formula (2) can be prepared, for example, from a method similar to the preparation of the vinyl ether compound of formula (1) above, starting from the preparation of a cycloaliphatic epoxy compound containing M of the following formula ^, c4i 0 (1 ~ cph • s

Where R6 is equivalent to an organic group as defined above, which is to react those containing suitable hydroxyalkyl vinyl ethers, or to convert the free hydroxy K formed in this reaction into a glycidyl ether group in a conventional manner or The hydroxyl group is reacted with the desired diisocyanate R4 (NC0) 2 and Rs 0H alcohol. Typical suitable cycloaliphatic epoxy compounds are

-15- This paper wave scale is applicable to the Chinese national falcon (cns) a4 specification (210x297 mm) binding line (please read the notes on the back side and then fill out this page) A7 ___B7 5. Description of the invention (tf)

--------- ^ ------ 玎 ------ ^ (Please read the precautions on the back before filling in this page) -16-The size of this paper is applicable to the Chinese National Standard (CNS ) A4 specification (210X297 mm) A7 B7 5. Description of the invention ([0 〇II -C-0-CH2- h3c · ο II -co-ch2- ooo II II -CH2-0-C- (CH2) 4- C-〇-CH2- h3c · --------- ^ — (Please read the precautions on the back before filling this page) 0: oo 11 II -CH2-0-C- (CH2) 4-C -〇-CH2- ο ο Order 17- This paper wave scale is applicable to Chinese national standard (CNS & A4 specification (210X297 mm) 322469 V. Invention description (/ [) ο 1 Ηc IIc 2 Η V__I

The value of AZ 3 in the compound of formula A refers to the better compound base under the compound of general compound \) / 4 / (V or 4 or 2 is the integer 4 2 to I 2 of the better compound number ο It is st. The number of objects is normalized ο Formula 1 under and to contain, 2 is 1 for, or both are adjusted 1 oy strong for and other UVX characteristics

one ο or binding line (please read the notes on the back before filling this page)

Ο — (CH2) — Ο-CH: CH2 Ο —— (CH2) — Ο-CH = CH2 一一 孓 — This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of invention (〆where s is an integer from 2 to 10, especially 2 or 4. Another preferred form of those vinyl ether compounds is where A is a group of formula (4), R14 and R1 ^ are both hydrogen atoms and z is 1. The method for preparing the compound is well known to those skilled in the art. For example, the formula [H2 C = CH-Ο-] zA where A is the formula (3) can be prepared, for example, from the formula HOOC-CD1] A CH3 or HOOC — CD1] —C00H carboxylic acid, where [D1] is the formula-(CxHzx)-CH = C Η-[(C uH 2 u])-c H = CH_] v— (CyH2 y) _ , U, v, x and y are also as defined on M, or start from the corresponding fatty acid ester, for example, corresponding to methyl ester, which is firstly oxidized in situ with peracid in the known way in the conventional manner. The acid or ester is therefore converted into the corresponding epoxy compound and then reacted with the desired alkyl alkyl vinyl ether of the formula H2 C = CH_0 — (CsH2 s) — 0H to form the formula HzC = CH — 0 — (CsH 2 s)-0〇C — [D] A CH3 or formula Hz C = CH-〇- (C sH 2 s)-OOC-CD]-COO-(C sH 2 s) ~ 〇 ~ CH = CHz 0 Similarly, in the preparation of vinyl ether compound of the following formula -19 This paper scale is applicable to the Chinese national standard falcon (CNS) A4 said grid (210X297 male thin) --------- ^- ---- IX ------ ^ (Please read the precautions on the back before filling in this page) A 7 B7 5. Description of the invention (丨 浐) R14

0II H2C = HC-0-(Q H2s) — 0 — C — (Ct h2 > (4) ^ [E] Factory

CH

The starting material used for CH R 15 may be the compound of the formula R14 ΟR ^ C — ((; Η2 ()-ν (CtH2t)-^-Υ ^ Γ

R 15 (Please read the precautions on the back before filling this page)-Binding _ where R1 s is a hydrogen atom or an alkyl group, such as methyl, the rest of the symbols are as defined above, the compound can follow the similar epoxidation reaction and the desired Formula H2 C = CH-0-(CsHz s)-OH vinyl ether to carry out the reaction. The vinyl ether compound of the present invention represents a useful formulation ingredient of a composition that can be hardened by light. The invention therefore also relates to its use as a polymerizable component of this composition. This composition also includes one or more effective amounts of the photoinitiator described under K, for example from 0.5 to 20% by weight, based on the weight of the composition, preferably one or more ethylene of the present invention In addition to the basic ether compound and one or more initiators, it also includes at least not the vinyl ether compound of the present invention-2 0-This paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (210X297 public shame) A7 B7 V. Description of the invention (1) The polymerizable compound of 1 1 0 1 1 The additional polymerizable compound available is, for example, a conventional white base 1 1 polymer compound > the general amount is 0 to 80% by weight. The total composition of Μ is ^ -Ν Please first 1 1 quasi t such as monoacrylate f diacrylate * and propionate functional groups number 1 | Polyacrylates of up to 9 or corresponding methacrylates f M and B Sj 1 Note 1 Vinyl compounds with up to 6 alkenyl functional groups Matter 1 | Suitable mono (meth) acrylates are »for example allyl acrylate then 1 9 allyl methacrylate methacrylate 9 ethyl acrylate propylene page cover 1 acid n-propyl ester n-butyl acrylate Isobutyl acrylate n-hexyl acrylate S_ ^ 1 I ί Acrylic acid 2 — ethylhexyl acrylate n-octyl acrylate n-decyl acrylate and 1 1 I n-dodecyl acrylate methyl methacrylate ethyl methacrylate ethyl 1 1 group N-propyl propionate, n-butyl methacrylate, n-butyl methacrylate, isobutyl methacrylate 1 f n-hexyl methacrylate, methacrylic acid 2 monoethylhexyl methyl propionate 1 I n-octyl methacrylate * n-decyl acrylate Ester and n-dodecyl methacrylate 1 I Acrylic acid 2 — hydroxyethyl acetate acrylic acid 2 — hydroxypropaneacrylic acid 3 — 1 1 hydroxypropyl methacrylate 2 monohydroxyethyl methacrylic acid 2 — Hydroxy thread 1 Propyl ester> Methacrylic acid 3 — Hydroxypropyl acetate Acrylic acid 2 monomethoxy ethyl 1 | Acrylic acid 2 — Ethoxy ethyl ester and acrylic acid 2 — Ethoxy propyl ester or propylene 1 1 Acid 3 — Ethoxypropyl ester $ Tetrahydrofurfuryl methacrylate> Acrylic acid 2 — (1 1 2 — Ethoxyethoxy) ethyl methacrylate cyclohexyl t acrylic acid 2 1 1 — phenoxyethyl acetate acrylic acid Glycidyl acrylate and isodecyl acrylate $ Appropriate 1 | A single N-vinyl compound is N-vinylpyrrolidine_ or N-ethyl 1 I hexamethylene amide 0 This product is also known as part t Goods> For example, from 1 1 I-2 1-1 1 1 This paper size is applicable to China National Standard (CNS) A4 specifications (210X297 mm) A7 322469 ________B7 V. Description of invention (y) Available by SARTO M ER Get. Further suitable di (meth) acrylates are, for example, cycloaliphatic anti-diol or aromatic diol di (meth) acrylates, such as 1,4-dihydroxymethylcyclohexane, 2,2-bis ( 4 Monohydroxycyclohexyl) propane, bis (4 monohydroxycyclohexyl) methane, hydrogen, 4,4'-dihydroxybiphenyl, phenol A, bisphenol F, bisphenol S, ethoxylated or propoxy Bisphenol A, oxylated or propoxylated bisphenol F or ethoxylated or propoxylated bisphenol i S 0 Such di (meth) acrylates are known, some of which are also commercially available Can use formula (4), (5) * (6) and (meth) acrylate compound ^ si (4), (please read the note on the back first # 'Item 4 fill in this page V— • install

Ο Ο

OH

ο ο ο 〇-line ⑺

OH 22

This paper scale is applicable to China National Standards (CNS) Α4 specifications (210X29 * 7mm) A7 B7 5. Invention description (y {) where S! Is hydrogen or methyl,

Yi is a direct bond, (Ci —cs) alkylene, — S—, —0 —, one SO —, — S〇2 — or one c〇 一,

Si 0 is (Ci —c8) alkyl, unsubstituted or substituted with one or more (Ci -C4) alkyl, hydroxy or halogen atom substituted phenyl, or is -C Η 2-0 S 1 1, wherein Si is (Ci-C8) alkyl or phenyl, and A: is a group selected from the following formula

CC0C0C The di (meth) acrylates of formulas (4) and (5) are known and some are commercially available, such as SR®349 or Novacure® 370. Ethylated bisphenols, especially ethyl Oxylated bisphenol A or dicyclopropyloxy ether of bisphenol, especially dicyclopropyl ether of bisphenol A, reacts with (meth) acrylic acid to form compounds of formula (4) and (5). It is also possible to prepare the compounds of formula (6) and (7) by the same method, which is the diglycidyl ether of reaction (6 a) ---------- ^ ------. 玎- ----- ^ (Please read the notes on the back before filling this page)

This paper scale is applicable to China National Standard (CNS) A4 (210X297mm) V. Description of invention (> /) A7 B7

This paper wave scale is applicable to the Chinese National Standard (CNS) A4 specification (210X: 297 mm) ^ 22469 A7 B7 V. Description of the invention (^ s) These compounds are known, and some of them have been commercialized. For example, compounds of formulas (8) and (9) can be obtained by conventional methods using cycloaliphatic diepoxides of formulas (8a) and (9a)

〇〇 > (8a)

(9a) React with (meth) acrylic acid to form compounds of formula (8) and (9) respectively. The compound of formula (11) can be obtained from Kayarad® R-604. Further suitable poly (meth) acrylates are, for example, monomeric or oligomeric fatty, cyclic or aromatic acrylic or methacrylic esters, whose (meth) acrylate functional groups are greater than 2, especially 3 , 4 or 5 functional acrylate or methacrylate. A suitable fat pad multifunctional (meth) acrylate is, for example, -25- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) binding line (please read the precautions on the back before filling in this Page) A7 B7 V. Description of the invention (<) 1 1 Alkanes — 2 9 4 9 6 — Triols> Glycerol or 1 ♦ 1 9 1 — Trimethylolpropane 1 1 Triacrylate and trimethyl ester Acrylate 9 Ethoxylated or propoxylated 1 1 Glycerin or 1 f 1 9 1 — hydroxymethyl propane and hydroxyl-containing tri (methyl — please first 1 1) acrylic ester 9 which is derived from tricyclic Oxygenated compounds as revealed by triols-Read 1 Back 1 Reaction of epoxypropyl ether with (meth-) acrylic acid. It is also possible to use, for example, face 1 Note Pentaerythritol tetraacrylate * Bistrimethylol propane 4 Acrylic acid pentapentyl | 1 item | Tetral monohydroxy tri Enoic acid ester or pentaerythritol monohydroxy trimethacrylate re | | or dipentaerythritol monohydroxy pentaacrylate or dipentaerythritol monohydroxy pentamethacrylate 1 acrylate on this page is also possible Use functional group polyurethane acrylic acid 1 1 I vinegar or polyurethane methacrylate. The polyurethane (methyl 1 1 order 1 —) acrylate can be prepared in the art for those skilled in the art Known methods such as the reaction of hydroxyl-terminated prepolymers with hydroxyl-based (methyl—) acrylic esters 1 | formation of polyurethane (methyl—) acrylates 0 1 I suitable aromatic trio (methyl—) Acrylic acid esters are, for example, dihydric phenol I 1 triglycidyl m 9 and three hydroxyl-containing phenols or cresol phenolic products with (methyl thread 1 —) acrylic acid 0 1 | The finished product preferably includes at least one liquid (meth) acrylic ester f containing 1 to 9 acrylic functional 1 I groups, especially an aromatic emulsifier including 1 to 9 acrylic ester 11 functional groups »Fatty or cycloaliphatic ( Meth) acrylate C 1 1 Furthermore ♦ The composition of the present invention may include m 1 as an additional polymerizable component | ionic polymerizable organic substance f usually used in an amount of 0 to 8% by weight 9 1 I Μ total composition weight Subject to this kind of additional ingredients, especially epoxy compounds 9 1 1 |-26-1 1 1 This paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (210X297 public shame) A7 __ _B7 V. Description of the invention (<) Preferred are compounds that can flow below about 10 to 3 Ο υ. The epoxy resin used in the composition of the present invention is generally a compound having an average of 1 '2-epoxy groups in the molecule. Such resins may have a fat, aromatic, cycloaliphatic, aromatic or heterocyclic structure; the resin contains an epoxy group as a pendant, or the epoxy group becomes a fat or heterocyclic ring system Part of. Such epoxy resins are generally known and commercialized. Examples of this type of epoxy resin are as follows: I) Polyepoxypropyl and poly (yS-methylepoxypropyl) esters, which can be prepared in compounds containing at least two carboxyl groups and epoxy Chloropropane or glycerol dichloropropane or point-methylepoxypropane, the reaction is conveniently carried out in the presence of a base. The compound containing at least two carboxyl groups in the molecule is suitably a fatty polycarboxylic acid. Examples of such polycarboxylic acids are glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or Dipolymerization or trimerization of dilinoleic acid. However, it is also possible to use cycloaliphatic polycarboxylic acids, such as tetrahydroteteic acid, 4-methyltetrahydrotitanate, hexahydrophthalic acid, or 4-methylhexahydrotetracarboxylic acid. Aromatic polycarboxylic acids can also be used, typically titanic acid, isotitanic acid, terephthalic acid, trimellitic acid or pyromellitic acid. It seems that it is also possible to use carboxyl terminal adducts, such as trimellitic acid and polyols, such as glycerin or 2,2-bis (4-hydroxycyclohexyl) propane Ο-27- This paper size is suitable for China National Standard (CNS) Μ 说 格 （210Χ297mm） IIIIIIII Packing-IIIII Order II equipment · {Please read the precautions on the back before filling in this page) A7 B7__ V. Description of invention (^) II) Polyepoxypropyl or poly (/ 3 -Methylepoxypropyl) ether, which can be prepared by reacting a compound containing at least two free hydroxyl and / or phenolic hydroxyl groups with a suitable substituted epichlorohydrin, the reaction is performed under alkaline conditions or in the presence of an acid catalyst Under, followed by a base treatment. Such ethers are derived from, for example, acyclic alcohols, typically derived from ethylene glycol, diethylenedioxide and higher poly (oxyethylene glycol), 1,2-propylene glycol or poly (oxypropylene glycol), 1,3 — Propylene glycol, 1,4-butanediol, poly (oxytetramethylene glycol), 1,5-pentanediol, 1,6-hexanediol, 2,4,6-hexanetriol, glycerin , 1 * 1, 1-trimethylolpropane, bistrimethylolpropane, pentaerythritol or sorbitol, and derived from polypropylene epichlorohydrin. However, it can also be derived from cycloaliphatic alcohols * such as 1,3-dihydroxycyclohexane or 1,4-dihydroxycyclohexane, bis (4-hydroxylhexyl) methane, 2,2-bis (4 A hydroxycyclohexyl) propane or 1,1 bis (hydroxymethyl) cyclohex-3-ene, or containing an aromatic nucleus, such as Ν, Ν—bis (2-hydroxyethyl) aniline or p, p Bis (2-hydroxyethylamino) diphenylmethane. Epoxy compounds can also be derived from nuclear phenols such as resorcinol, hydroquinone or hydrogen rat or based on polynuclear phenols such as bis (4-hydroxyl) methane (bisphenol F ), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) or is obtained from the condensation of phenol or cresol and formaldehyde under acidic conditions, such as phenol novolac and cresol novolac. III) Poly (Ν-epoxypropyl) compound, for example, can be prepared in the ring-28 * This paper standard is applicable to China National Standards (CNS) Α4 specifications (210X297 mm) binding (please read the note on the back first Please fill out this page again) Μ ^ 22469 Β7 5. Description of the invention (> 1) The reaction product of oxychloropropane and an amine containing at least two amine hydrogen atoms is dehydrochlorinated. These amines are for example n-butylamine, aniline, toluidine, m-xylylenediamine, bis (4-aminophenyl) methane, amine or bis (4-methylaminophenyl) ) Methane. However, poly (N-epoxypropyl) compounds also include N, N'-diepoxypropyl derivatives of cycloalkyl ureas, such as ethylene urea or 1,3-propenyl urea, and hydantoin The N, N diglycidyl derivative is typically 5,5-dimethylhydantoin. IV) Poly (S-epoxypropyl) compounds, preferably bis (S-epoxypropyl) derivatives, derived from disulfide, such as 1,2-ethanediol or bis (4-hydrogen Thiomethylphenyl) ether. V) The epoxy group forms an acyclic or heterocyclic ring part of the epoxy group. Examples of epoxy compounds are bis (2,3-epoxycyclopentyl) ether, 2,3-epoxy ring Amyl glycidyl ether, 1,2-bis (2,3-epoxycyclopentyloxy) ethane, bis (4-monohydroxycyclohexyl) methanediglycidyl ether, 2,2-bis (4 monohydroxycyclohexyl) propane diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-6 —Methyl-cyclohexylmethyl-3,4-epoxy-6-methylcyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, bis ( 3,4-epoxy-6-methyl-cyclohexylmethyl) adipate, ethylene bis (3,4 epoxycyclohexane carboxylate), ethylene glycol di (3,4 —Epoxycyclohexylmethyl) ether, vinylcyclohexene dioxide • Dicyclopentadiene diepoxide or -29- This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm ). (: F gutter (please read the notes on the back first (Fill in this page again) A7 __B7_ V. Description of the invention 2-(3,4-epoxycyclohexylmethyl-5,5-spiro-3,4-epoxy) cyclohexane-1,3-dioxa However, it is also possible to use epoxy resins with 1,2-epoxy groups attached to different heteroatoms or functional groups. These compounds typically include N, N, 0-triepoxypropyl derivatives of 4-aminophenol , Glycidyl glycidyl ether of salicylic acid, glycidyl ester, N-glycidyl-N '-(2-glycidoxypropyl)-5,5-dimethylhydantoin or 2-epoxypropyloxy-1,3-bis (5 * 5-dimethyl-1-1-epoxypropylhein-3-yl) propane. In addition, such epoxy resins are hardened The liquid pre-reacted adduct of the agent is also suitable for use with epoxy resins. Of course, the composition of the present invention may also use an epoxy resin mixture. Regardless of the polymerizable group of the components in the composition of the present invention, the photoinitiator used may be Both are free radical photoinitiators and photoinitiators for cationic polymerization, K and a mixture of one or more of these initiators. The timing of using free radical photoinitiators is special It is when the composition of the present invention has carbon-carbon bismuth, especially when the compound has acrylate, methacrylate and vinyl. In general, any type of light initiation may also be used The photoinitiator will form free radicals under proper light. Typical conventional photoinitiator compounds are benzoin (be η ζ 〇i η), such as benzoin, benzoin ether, such as benzene Acetoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, benzoin phenyl ether and benzoin acetate, acetophenones, such as acetophenone, 2,2-dimethyl Oxyethylated benzene and 1,1-dichloroacetylated -30- This paper scale is applicable to China National Standard (CNS) A4 (2 丨 0X297mm) ^ IIIIIII Pack — IIII Order IIIII 4 '(Please read first Note on the back and then fill out this page) A7 B7 5. Description of the invention (>? |) Stupid, benzil, (benzil), benzil ketals (benzil ketals), such as stupid brewed dimethyl Ketal and benzoyl diethyl ketal, anthraquinone, such as 2-methyl quinone, 2-ethyl quinone, '2-tertiary monobutyl Sticks, 1 monochloro chloride and 2-pentyl roller, also including triphenylphosphine, phenylphosphine oxide, such as 2,4,6-trimethylbenzene diphenyl oxide knee (Luzirin® TP0), Benzophenones (benzophenones), such as benzophenone and 4,4'-bis (Ν, Ν'-dimethylamino) benzophenone, thioxanthones (thioxanthones) and xanthenes, Acridine derivatives, phenazine derivatives, quinoxa derivatives or 1-phenyl-1,2-propane dihedral 2--0-phenyl oxime, 1-aminophenyl phenyl oxime or 1-hydroxyphenyl ketone For example, 1-hydroxycyclohexyl phenyl ketone, phenyl (1-hydroxy isopropyl) ketone and 4- isopropyl phenyl (1-hydroxy isopropyl) ketone, the above are conventional compounds. A particularly suitable photoinitiator generally using helium / cadmium laser as the light source is acetone, such as 2,2-dialkoxybenzophenone and 1-hydroxyphenyl ketone, such as 1-hydroxycyclohexylphenyl Ketone or 2-hydroxyisopropyl phenyl ketone (= 2-hydroxy-2,2-dimethylacetophenone), but especially 1-hydroxycyclohexyl phenyl ketone. Another type of photoinitiator commonly used for argon ion lasers includes benzoyl ketals' such as benzoyl dimethyl ketals. In particular, Mα-hydroxyphenyl ketone, benzoyl dimethyl ketal or 2,4,6-trimethyl phenyl phenyl diphenylphosphine oxide is used as a photoinitiator. Another type of suitable photoinitiator includes ionic dyes, a counter ion compound-3 1- This paper size is applicable to the Chinese National Standard (CNS) A4 grid (210X297mm). Binding I (please read the precautions on the back first (Fill in this page) 322469 A7 __B7 V. Description of the invention (> <? ≫) It can absorb light and generate free radicals that can initiate acrylate polymerization. The composition of the present invention containing an ionic dye_counter ion compound can therefore be hardened more diversely by adjusting the visible light at a wavelength of 400 to 700 nm. Ionic dye-counter ion compounds and their mode of action are known to the public, such as EP-A 223587 and USP 4, 7 5 1, 1 0 2, 4, 77 2, 5, 3 0 and 4, 7 7 2, 5 4 1 Said. Examples of suitable counter ion compounds of suitable seed dyes mentioned are the anionic dye iodonium complex, the anionic dye-dioxin, especially the cationic dye of the following formula-anionic acid compound

Where X + is a cationic dye, R ', R " are independently alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl'alkynyl, acyclic system or saturated or unsaturated heterocyclic Ring base. When the photoinitiator of the component has a cationic polymerizable group, especially an epoxy group or a vinyl ether group, almost any compound known in the art for this purpose can be used. These ingredients are, for example, nucleophilic weak anions; ^ salt, in fact, examples are pro | ^ salt (halonium salt), moth vine (iodosyl salt) salt or qi salt (sulfonium salt), for example, disclosed in EP-A 1539G4

Wind ^ (sulfoxonium salt), for example, disclosed in EP-A 35969, 44272, 54509, and 164314 or diazonium salt, for example, disclosed in US-A -3 2-This paper scale is applicable to China National Standard (CNS) A4 (210X297mm) IIIIIIIIII Order-carry on (please read the precautions on the back before filling in this page) A7 B7 5. Description of the invention (¾ 3, 708, 296. Other cationic photoinitiators are metal dicyclopentadiene compounds ( Metallocene) salts, for example, are disclosed in EP-A 94914 and 94915. A summary of other existing _salt starters and / or metal dicyclopentadiene compound salts can be found in the following literature: "UV-Curing, Science and Technology ", (Editor: SP Pappas, Technology

Marketing Corp., 6 4 2 Westover Road, Standard,

Connectcut, USA) or "Chemistry & Technology 〇f Uv & EB Formulation for Coating, Inks & Paints ", Vol. 3 (edited by P. κ, T · Oldring). The preferred photopolymerization of cationic polymerizable groups The starting agent is the compound of formula (12) * (1 3) and (1 4): (12) (id) — II IIIIIIII Set the I line (please read the precautions on the back side before filling in this cornel) Θ S —G7 LQw "-| © p -I ㊀ 1 ^ 1-I-〇2 LQy," 〇-II ㊉--11 I 〇4 L% Θ 〇5 Θ where G! * G 2 > G 3 * G 4 * G5, GS and G7 are independently -33- This paper scale is applicable to the Chinese National Standard (CNS> A4 specification (210X297 public daughter)> Five A7 B7 C6-Ci 8 aryl groups that are not substituted or substituted by suitable groups, L is boron, phosphorus, arsenic or antimony, Q is a halogen atom or anion LQm-some of Q can also be a hydroxyl group, and w is an integer, equivalent to the valence of L plus 1. Cs — C: 8 aryl Examples are phenyl, naphthyl, anthryl and phenanthryl. Any suitable substituents are alkyl groups, preferably 〇1_C6 alkyl groups, such as methyl, ethyl, n-propyl , Isopropyl , N-butyl, secondary butyl, isobutyl, tertiary monobutyl or various pentyl or hexyl isomers, alkoxy, preferably Ci-C6 alkoxy, such as methoxy, Ethoxy, propoxy, butoxy, pentyloxy or hexyloxy, alkyl sulfur, preferably Cx_C6 alkyl sulfur, such as methyl sulfur, ethyl sulfur, propyl sulfur, butyl sulfur, Amyl sulfur or hexyl sulfur, halogen, such as fluorine, chlorine, bromine or iodine, amino, cyano, nitro or aryl sulfur, such as phenyl sulfur. Preferably the halogen atom Q is T chlorine, especially fluorine. Good anion LQin-for

A s F B F 4 * K C F 3 SO3 _ is better. S b F 6 S b F 5 Of course, two or more urn groups are contained in the molecule, for example, a disulfur compound is a suitable initiator. Particularly preferred is a cationic photoinitiator of formula (14), wherein G G s and G 7 are phenyl or biphenyl or a mixture of two compounds. The better cationic light starter formula (1 5) also binds 4V _ (please read the precautions on the back before filling this page) 0 34 This paper size is applicable to China National Standard (CNS) A4 specification (2! 0X297 C) A7 B7 five-d (15), description of the invention (> G8 (FenG9) c + CT--d--where c is 1 or 2, d is 1, 2, 3, 4 or 5,

T is a non-nucleophilic anion, especially BF4--PF 6-, AsF > S b F 6 ~ »CF 3 S 0 3-> C 2 F s S03 ~« n — C 3 F 7 S 0 3 N — C 4 F 9 S 0 3 * n — C6 F13 S〇3 _ or n — C8 Fi 7 SO3 _, C 6 F 5 S 0 3 —, _ acid phosphorus, P〇4〇Wl23-, or _ Acid silicon (Si04〇Wl24-, G8 is π-aromatic and G9 is 7!-Aromatic Shito anion, especially cyclopentadiene anion. G8 is π-aromatic Shito and G9 is an example of redundant aromatic Shito anion in EP -A 94915 is disclosed. G8 is π-Aromatic rice is preferably exemplified by toluene, xylene, ethylbenzene, cumene (cumene), methoxybenzene, methylnaphthalene, pyrene (pyrene), Perylene, 1,2-stilbene, diphenylene oxide and diphylene sulfide. Particularly good examples are cumene, methylnaphthalene and , 1, 2-stilbene. The preferred anion T is PFs--AsFs-, SbF6-, CF 3 S 0 3 ~> C 2 F 5 S〇3 '* n-C 3 F 7 S 0 3- 35- This paper scale applies the Chinese National Standard (CNS) A < 4 specification (210X297mm ---------- ^ ------ ix ------ il (please read the precautions on the back first and fill in this page) 322469 A7 B7___ 5. Description of the invention (now Lu »η -C 4 F s S 0 3 _, n-Cs F ι 3 S Ο 3 * η- ~ 〇8 Fx 7 SO '° Jintide dicyclopentadiene compound salt can be used together with oxidizing agent. This use case is described In EP-A 1 2 6 7 1 2. In order to increase the light efficiency, it is also possible to use sensitisers according to the type of the starting agent, examples of which are polycyclic aryl aromatic hydrocarbons or aromatic ketone compounds, preferably A specific example of is disclosed in EP-A 153904. The photoinitiator is added in an effective amount, for example from about 0.1 to about 10% by weight, based on the weight of the mixture. When the mixture of the present invention is used in the stereolithography method, usually The use of laser beams is mainly due to the fact that the absorption capacity of the mixture must be matched with the type and photometricity of the photoinitiator, so that the hardening depth of the general laser speed is about 0.1 to 2.5 mm. The total amount of starting agent is preferably from 0 to 5 to 5% by weight. The mixture of the present invention may also include various photoinitiators having different photosensitizing effects on light rays of different wavelength emission lines. Good use of ultraviolet / visible light sources that emit different emission lines can achieve this goal. It is advantageous if different photoinitiators are selected and used in concentrations that produce the same optical absorption under the emission line. The addition of other ingredients to the composition of the present invention is generally advantageous, for example, as conventional additives, such as stabilizers, such as ultraviolet stabilizers * polymerization inhibitors, separating agents, wetting agents, flow agents, photosensitizers, anti-settling agents, surfactants , Dyes, pigments or fillers. The amount of the additive used individually can effectively achieve the desired purpose, and can constitute up to 20% by weight of the composition of the present invention -36- This paper size is quickly used in the Chinese National Standard (CNS > A4 specification (210X297 mm) binding service ( Please read the precautions on the back first and then fill out this page) ΑΊ Β7 5. Description of the invention ο If necessary, the composition can also contain up to 50% by weight of hydroxyl terminal polyether or polyester, such as difunctional or trifunctional Functional polyether or polyester-polyol, polytetrahydrofuran, hydroxyl-terminated polyurethane, or preferably poly-ε-caprolactam. The preferred composition includes 5 to 60% by weight of one or A plurality of vinyl ether compounds of the present invention; 0 to 40% by weight of mono-, di- or multi-functional acrylate or methacrylate; 30 to 80% by weight of di- or multi-functional epoxy compounds; 0 to 5% by weight of free radical photoinitiator; 0.5 to 5% by weight of cationic photoinitiator; 0 to 40% by weight of hydroxyl-terminated polyether or polyester; and 0 to 10% by weight One or more additives. The composition of the present invention can be prepared by adding K in a known method, such as Mixing the individual components and then mixing the pre-mix or mixing all the components with a conventional device such as a paddle type mixer is advantageously carried out without light, suitably at high temperature. The light-sensitive composition of the invention can be exposed to light Polymerization after irradiation with chemical rays, for example by electron beam X-ray, ultraviolet or visible light, in other words, by electromagnetic light or particle light with a wavelength of 280 to 6 50 nm. Particularly suitable for helium / cadmium, argon or nitrogen Laser beam, Μ and metal vapor and multi-frequency M dYAG laser. For this reason, those skilled in the art are familiar with a suitable photo-initiator Bi-37- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm ) II II III Order-Line II (please read the precautions on the back before filling in this page) 322469 Α7 Β7 V. Description of the invention () key please # ^^ 1 ^ '-., Vfi Rong Ministry of Economy The quasi-authorized Beigong Consumer Cooperative prints the committee to make it clear that Ben · ίν: · (whether or not to change the original substance after the amendment must be selected, and it is appropriate to sensitize each selected light source. It has been determined that light irradiation has penetrated into Aggregated The depth M and the operating speed of the product are directly related to the absorption coefficient and the concentration of the photoinitiator. In stereolithography, it is preferable to use the largest number of free radicals that can be produced by K and to allow the most light to penetrate into the polymerized formulation Photoinitiator. Therefore, the present invention is also a method for preparing a hardened product, in which the composition as described above is treated with actinic radiation. For example, the composition of the present invention can be used as a binder to coat the composition on the surface, Photoresist, such as solder photoresist, or rapid replication, especially three-dimensional lithography. The present invention also relates to a method for preparing a three-dimensional object from the composition of the present invention by means of lithography, especially three-dimensional lithography Method, in which the surface of the composition layer of the present invention is irradiated by the ultraviolet / visible light source in its entirety or in a predetermined form, so that the layer of the desired thickness is cured in the irradiated area, and then the composition of the present invention constitutes a new layer Formed on the cured layer, the new layer is irradiated as a whole or in a predetermined pattern, and the new layer and the irradiation are repeated, and the multilayer is bonded to each other Together with the cured layer constituting the three-dimensional object. In the above method, preferably a computer controlled laser beam is used as the light source. In general, the so-called green embryo model caused by the first light hardening as described above is not enough to become a solid, and then the final full hardening is carried out by heating and / or further light. -3 8 _ (please read the precautions on the back before filling in this page), vs. this paper standard is applicable to China National Standard (CNS) Α4 specification (210Χ297mm) A7 Five Ming Instructions

-The material. The wood material can be harder and harder when coated with M, and the material is formed into a clear coating. The surface is painted as a surface. It is formed by other objects or made of porcelain and Ming Tao, which belongs to Ruojin paper. The road was shot by Yin Meng and Yin Changyuan. Wave light meter suitable millisecond should be a system to the phase control rice brain and the micro-electric cover 1 The light is used directly from the connection, or the large image object can be combined with the convex and mixed lightness of the thick plate. Reprinted or coated with a combination of etheryl ethene under the formula 1 with examples to prepare C. (please read the precautions on the back before filling this page)-installed.

Order A) 1 1 1. 7 grams (Ο · 3 mol) of diglycidyl ether of bisphenol A (Araldit® GY250) in 1 2 0D and 5 2. 87 grams (0.6 mol) of hydroxyl groups Ethyl vinyl ether and 0.1 g potassium hydroxide were heated in nitrogen. Then, the mixture was stirred at this temperature for 12 hours and then at 150 ° C for 48 hours. B) The obtained 6 3 g (0 ♦ 12 cumulus) divinyl ether at 70 υ with 178 g (1.92 mol) epichlorohydrin and 1.57 g 50% tetramethylammonium chloride The solution (TMAC) was stirred for 1 hour. Then, under reduced pressure, 19.2 g of 50% sodium hydroxide solution (90 mbar; 79Ό) was added dropwise, and the formed water was separated by adding M in a water separator. When the water is completely separated, the excess epichlorohydrin is evaporated-3 9- This paper scale is applicable to the Chinese National Standard (CNS) Α4 wash grid (210Χ297 mm)> A7 B7 Fifth, the invention description phantom, residue It was absorbed in 200 ml of toluene. The formed sodium oxychloride was extracted with sodium bicarbonate solution and water after filtration. Finally, the organic phase was dried and the solvent was removed in a rotary evaporator. The desired product was 70. 8 grams (93 · 8%) of a viscous, brown resin with an epoxy content of 2.8 equivalents / kg (88.3% of the theoretical value). Example 2 Preparation of a vinyl ether compound containing the following formula

A) 156. 2 g (0.5 mole) of diglycidyl ether of bisphenol F (Araldit® PY250) at 88 ° C. with 88. 11 g (1.0 mole) of hydroxyl groups Ethyl vinyl ether and 0.17 g of potassium hydroxide were heated in nitrogen. Then, the mixture was stirred at this temperature for 12 hours and then at 1501C for 48 hours. B) The obtained 150 g (0.5 mol) of diethyl, ylhexyl ether at 70t and 499.54 g (5.4 mol) of epichlorohydrin and 4.5 g of 50% tetramethyl chloride The ammonium solution (tmAC) was stirred for 1 hour. Then, under reduced pressure, 54.4 g of 50% sodium hydroxide solution was added dropwise. * Separate, react and absorb water according to Example 1. The desired product is 1.148 g (78% of theoretical value) of viscous, yellow liquid resin, -40- This paper size is applicable to + National Standard (CNS) Α4% grid (21〇ϋ97 public shame) (please read the back first Please pay attention to this item and then fill out this page) -installation-, νδ line 87 Wuming description of weight and weight 5 5 2 is the value of the content of the base oxygen ring 7 The theory of the physical compound of the ether ether and the following formula 3 contains Example system

----------- installed-- (Please read the precautions on the back before filling in this page) A) 101. 13 grams (0.5 mole) of bisphenol A diglycidyl ether (Araldit® DY026) was heated at 12 ° C with 88.11 g (1.0 mol) of hydroxyethyl vinyl ether and 0.17 g of potassium hydroxide in nitrogen. Then • The mixture was stirred at this temperature for 12 hours, then at 150 ° C for 48 hours. B) The obtained 150 g (0.39 mol) of divinyl ether at 70t: with 569 · 6 g (5,96 gm) of epichlorohydrin and 5.1 g of 50% tetramethylammonium chloride The solution (TMAC) was stirred for 1 hour. Then, under reduced pressure, 59.2 g of 50% sodium hydroxide solution (90 mbar) was added dropwise, and water separation, reaction and post-Burmese steps were carried out according to Example 1. The desired product was 159.5 g (83.5%) of a colorless liquid resin with an epoxy group content of 3.52 equivalents / kg (86 · 2% of theoretical value) 〇-4 1-This paper size is applicable to Chinese national standards (CNS) A4 present (210x297 public shame) ^ 22469 Μ Β7 5. Description of the invention (Example 4 Preparation of vinyl ether compound containing the following formula 〇CJ A) According to Example 1, 158 ♦ 08 grams (1 ♦ 0 mol) Phenyl glycidyl ether reacts with 88.11 g (1.00 m) of hydroxyethyl vinyl ether and 0.34 g of potassium hydroxide. B) According to Example 1, 100 g (0.42 mol) divinyl ether was obtained with 62 1.2 g (6.17 m) epichlorohydrin and 5.59 g 50% Methyl ammonium chloride solution (TMAC) reaction. After adding 67 · 2 g of 50% sodium hydroxide solution dropwise, according to the separation and subsequent steps of water in Example 1, the desired product is 1 1 6 · 4 8 g (94% of theoretical yield) of slightly yellow liquid resin. The oxygen content is 3.4 equivalents / kg (87% of theory). Example 5 Preparation of a vinyl ether compound containing the following formula CH, w〇 丫 0 丫 0 ~ 〇 / 〇 = < ΝΗ (please read the precautions on the back before filling this page)

ΗΝ 又 I

NH CH〇CH „NH ^ O ^ ° -42 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ΑΊ Β7 V. Description of invention (flat () 65 · 89 g (0 · 38 mol) Toluene diisocyanate at 35¾ and 0. 33 grams of 2,2'-methylidene bis (6-tertiary butyl 4-methylphenol) (Ra 1 ox®46)-stirring and heating * And dropwise add 43.93 g (0.38 mol) of ethyl acrylate. The mixture was stirred at 3 5¾ for 8 hours until the isocyanate content was 3.4 equivalent / kg. Then, 100 g ( 〇. 19 mol) Example 1 A) divinyl ether was dissolved in 100 ml of toluene, added dropwise. After 3 5Ό for 4 hours, the isocyanate content was measured to be 1.17 equivalents / kg .Add another 0.24 g of dibutyl thionate laurate, after 35 ¾ for 2 hours * The isocyanate content is 0. 07 equivalent / kg. Remove the solvent in a rotary evaporator, and the residue is dried under high vacuum . The desired product is 200 g (9 5% of theoretical yield) very viscous yellow resin. GPC shows a molecular weight of Mn = 1430; Mw = 6850 ° 6 bookbinding system (Read Notes on the back and then fill the page) prepared containing a vinyl ether compound of the formula

-43- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 322469 A7 B7 5. Description of the invention 3 3 7 grams (0.19 in 35¾ and 0.25 grams Ra, and added drop by drop 1 1.25 g. After cooling the reaction mixture, after 50 minutes, 50 ml of diethylene (2.99 equivalents / kg mole) of Example 1A) was added dropwise. After the reaction mixture was added with 0.12 g of dibutylsulfonium for 4 hours, the isocyanate content of the solvent was removed in a rotary evaporator, until the desired product was 87.8 g of thick yellow resin. GPC showed 7 8 8 0 ° 萁 耳) A 1 ο X ® 4 (0-19 temperature does not exceed toluene, measured. Then, 5 ethers are dissolved in 4 5 persevere cinnamate, the mixing reduced to 0 · Residue in high (92% Μ η = 1 2 phenylene diisocyanate 6-stirring, heating moles) 6 0 ° C solution 0 grams (50 milligrams of the mixture in 0 4 The theoretical vacuum produces 70% of allyl alcohol. After 4 hours of isocyanate 0-097 liters of toluene 4 hours, and then 3 5 υ holding capacity / kg. Medium dry. Yield) very sticky M w = Example 7 A vinyl ether compound Wo Yaya containing the following formula was prepared. 〇B °

> = ° 〇 == (

〇 NH 0

GD. Binding 4 '(please read the precautions on the back before filling in this page) -4 4-This paper size is applicable to China National Standard (CNS) A4 specification (210X297 public daughter) Μ Β7 5. Invention description (^ fj) 67 · 42 g (Ο.387 mol) of salt at 35t with 0 · 5g Ra 1 ox®4, and slowly add 58 · 13g (0 · cyclodecyl alcohol E (H0ECHEST) drop by drop. Cold internal temperature No more than 35 deaths. After 1 * 5 small cyanate content is 3 · 08 equivalents / kg. M mixture, then, 1000 g (0.19) of divinyl ether is dissolved in 100 ml of toluene reaction mixture at 4 5 C was continuously stirred for 8 hours, 0.35 equivalents / kg. After adding 0.24 g, the mixture was continuously stirred at 3 5 C for 4 hours. The mixture was reduced to 0.06 equivalents / kg. The residue was dried under high vacuum in the rotary evaporation. To obtain the desired product (9 2 * 9% of the theoretical yield) very viscous measured Mn = 122〇; Mw = 5130 Example 8 Preparation of a vinyl ether compound containing the following formula

Toluene diisofluoric acid 6-stirring, heating 3 8 7 mol) of the reaction mixture, after time, the solution was diluted with 50 ml of toluene (3 mol) Example 1 A, after adding dropwise. The isocyanate content is dibutyl thorium laurate, the solvent is removed from the isocyanate content reducer, and the residue is 209 · 5 grams of yellow resin. Use GPC to bind the gutter (please read the notes on the back before filling this page)

〇〇 \ _1 \ This paper wave scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of invention (ί | 4) Α) According to Example 1, 137.3g (0.5mol) 3,4 — Epoxycyclohexylmethyl-3 ′ — 4 ′ _epoxycyclohexane carboxylate (

Araldi t®CY179) was reacted with 88.11 g (1.0 mol) of hydroxyethyl vinyl ether and 0.07 2 g of potassium hydroxide. (B) According to Example 1, 150 g (0.35 Molar) divinyl ether reacts with 5 18.1 grams (5.60 mole) of epichlorohydrin and 4.66 grams of 50% tetramethylammonium chloride solution. After 56g of 50% sodium hydroxide solution was added dropwise, the water separation and post-pressing steps were carried out according to Example 1, to obtain the desired product as 153 * 8g (80 · 9% of theoretical yield) of light brown liquid resin, epoxy The base content is 2.34 equivalents / kg (63 · 1% of theoretical value). Example 9 A vinyl ether compound containing the following formula 〇〇 (0Η2) 4-Α〇 ^ Ο 〇-L o / \ / one \ / \ A) according to Example 1, 161.1 g (0.4 mol) The following cycloaliphatic epoxy resin (Ara 1 dit® CY177) -46- This paper wave standard is applicable to China National Standard (CNS) A4 specification (210X297mm) binding line (please read the precautions on the back before filling this page ) 322469 7 A7 _ ^ _ £ V. Description of the invention (/ 0 〇〇 < r reacted with 70 · 5 g (〇 ♦ 8 mol) of hydroxyethyl vinyl ether and 0.058 g of potassium hydroxide. B) Example 1, the obtained 150 g (0,2 3 mer) divinyl ether and 340.47 g (3.68 mol) epichlorohydrin and 3.06 g 50% tetramethylammonium chloride Solution reaction. After adding 36 g of 50% sodium hydroxide solution dropwise, the water separation and subsequent steps were carried out according to Example 1, and the desired product was 1 13.7 g (75.5% of theoretical value yield) of light brown liquid resin, The epoxy group content is 1.04 equivalent / kg (34.1% of theoretical value). Example 10 Preparation of vinyl ether compound A containing the following formula) 43.46 g (0.31 mol) of cyclopentene acetate methyl ester was dissolved in 80 ml of chloroform, after adding 4 g of sodium acetate, 82.5 g The 40% peracetic acid solution (in acetic acid) was added with stirring, and the temperature was maintained at about 3 5¾. Then, the reaction mixture was stirred at 35D for another 5 hours. The reaction mixture was extracted with 5% sodium bicarbonate solution and extracted twice with water. Separate the organic phase, dry it, and destroy the residual peroxide with sodium sulfite-4 7- The paper size is applicable to China National Standards (CNS) A4 specification (2 丨 0 X 297 mm) IIIIII Packing—I Stranding (please first Read the precautions on the back and then fill out this page) Α7 Β7 V. Description of the invention (ψι) * 29-87 g (0 ♦ 3 8 propyl titanium oxide in methanol, so that the residue will be dissolved in vinegar with water after high vacuum Extraction. 2 · 2 3 g (GC 98%). After distilling the organic phase, pentene methyl acetate (66 · Β) is in a sulfonated flask equipped with a stirrer, distillation unit and epoxide with 44 · 43 Ether and 0. 04 grams of four different heat. Separation of 6.7 grams of methanol formed by careful distillation. Natural hydroxybutyl vinyl ether. Extracted with sodium hydrogen acid solution, then, the solvent was removed to obtain 4 (9 2.5% of theoretical value) grams of Igreux column (〇.19 mole) mol) hydroxybutyl ethylene is refluxed and nitrogen is added for about 1 hour, and excess ethyl acetate has been distilled in 8 0¾ In the use of 5% carbon in the rotary evaporator auxiliary epoxy vinyl ether)). Example 1 1 Preparation of vinyl ether compound containing the following formula

3 2 .3 grams of 3,4_epoxy ring 5% theoretical value were obtained). Thermometer and binding with V (Please read the precautions on the back before filling this page) §. H3C- (CH2) 7 -CH-CH- (CH2) 7-C00 (CH2) 4-0-CH = CH2

V A) According to R.F. Storey, T.P. Hickey; J. Polym. Sci. A,

Polym. Chem. 31 (1993), pl825, first dissolve 1 48.24 g (0.5 mole) methyl oleate (technically a mixture of isomers) £? T in 300 ml of chloroform . Then add 255 g (0.6 mol) 8% sulfuric acid, 4 g (◦ · 0 1 mol) trioctyl methyl ammonium chloride (-4 8-This paper scale is applicable to the Chinese National Standard (CNS) Α4 specifications (210Χ297mm) A7 B7 V. Description of the invention (屮) A 1 iquat ® 3 3) Sodium tungstate hydrate and the substance are stirred at 60 t for 5 hours, the sodium solution and water are extracted, dried and dried in a rotary evaporator Removed in the middle of the hour, to obtain orange brown 1 3 * 03 equivalent / kg (B) in a sulfonated enthalpy bottle equipped with a stirrer, distillation device dissolved in 100 ml of methylbenzyl) hydroxybutyl vinyl mixture in 1 0 5 ° C heated mixture. Hold on to the reaction and stop (about 11 hours). In addition to dissolving the residue in dichloromethane, the residue was dried in a rotary evaporator to obtain a yield of 6 3 (GC about 94% • 2 g (• 0 5 its separation of organic phase sodium sulfate residue in high grams Product,% Theoretical value contains V ig (Ο '1 3 7 · 1 7 4 grams of second search, steamed 6), 8 9 grams (0, then dried, with sub-solvent, residual 5 5 · 7 9 4-7 To the thermometer and β 0 g, add ether and 3 ·, and keep until the GC cannot detect the excess hydroxybutyl. * With the help of the above, remove the solvent to remove the desired product (9) 0 0 . 0 2 5 moles) squamous acid. Mix and dry with 5% hydrogen carbonate residual peroxide degree in vacuum 2 its epoxy content is) ° 6 ears of reu X column) epoxidized 7 g ( 0 · 3 2 Butyl tin oxide. After distilling off the methanol and toluene, the starting reactant is vinyl ether, sodium bicarbonate and water extraction, 9 · 2% of theoretical value III in high vacuum. (Notes and fill in this page again) Example 1 2 Preparation of vinyl ether compound H3C- (CH2) 4-CH-CH CH ^ CH-CH- (CH2) rCOO (CH2) 4-〇-CH containing the following formula = CH2

VV -49- The standard of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) A7 B7 5. Description of the invention (& A) A) According to the method of similar example 1 1A), 143 · 9g (Ο · 49 Mol) linoleic acid methyl ester with 1 008 · 72 g (2.39 mol) 8% hydrogen peroxide in the addition of 8 * 86 g 并 1 丨 (! 1_1 & seven © 336, 16 · 06 g (0 · 025 mol) _acid sodium reacts with 9.59 g phosphoric acid. The solvent is removed to obtain a product with a yield of 1 54 2 g (96.4 theoretical value), the epoxy content of which is 4.15 eq / kg (6 7.7% of theoretical value). Β) Similar to Example 10B) method, 148 · 76 g (0.456 mol) epoxide and 76.99 g (0.68 mol) hydroxybutyl vinyl ether and 0.2 1 g of tetraisopropyl titanium oxide reacted. After about 11 hours, the separation of formazan was stopped, and 1 79 · 27 g of the desired product (95 * 5% of theoretical yield) was isolated. Example 1 3 Preparation of vinyl ether compound containing the following formula Binding service (please read the precautions on the back before filling this page) Ο

Α) According to a method similar to Example 1 1Α), 120 g (0.788 mol) 5-carbomethoxy-2-orthoborneene and 807.8 g (1.9 mol) 8% hydrogen peroxide in Add 6.37g

Aliquat® 336, 13.7 g of sodium hexanoate and 7.12 -5 0-This paper size is applicable to China National Standard (CNS) Α4 specification (210Χ297 mm) 322469 A7

5. Description of the invention (ιή) Gram phosphoric acid reaction. Distillation under reduced pressure yielded an epoxide with a yield of 5 6.8 g (4 2 'theoretical value). B) Similar to Example 10B) method, 56 g (0.336 m3) of epoxide and 77.4 g (0.66 m) of butyl butyl vinyl ether and 0.2 g of tetraisopropyl oxide Titanium reaction. After removing excess methylbutyl vinyl ether, the organic phase was extracted as described in the example, 92 g of yellowish liquid was separated, and 20 g of this liquid was distilled to obtain the desired cyclodrenyl ether (0.5 mbar pressure Boiling point is 116 ~ ^ Example 1 4 Preparation of vinyl compound containing the following formula

A) According to the method of similar example 10A), 50 g (〇 ^ · 3) cyclohexyl 3-ene carboxylic acid methyl ester and 171.1 over 10 6 Mo with: _ (醏) reaction, after distillation, the yield is 38.9¾ f epoxide in acid (6 9 value). 1 Li round B) similar to Example 10B) method, 38 grams (〇 · epoxide with 56.6 grams (. 486 moles) based ether and 0.13 grams of tetraisopropyl titanium oxide. Min (8 0 % Theoretical value output) Orange liquid desired product-5 1-This paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm) A7 B7 5. Description of the invention (p) Color liquid. Example 1 5 Preparation contains the following formula Vinyl ether compound Ο

A) According to the method of similar example 10A), 168.80 g (0.8 kg) dimethyl tetrahydrotitanate was reacted with 230 · 1 of 40% peracetic acid solution (in acetic acid) and 10 g of sodium acetate to obtain The yield is 114 · 2 g (62.7% of theoretical value) of epoxide, and its epoxy group content is 3.3 equivalent / kg (72.7% of theory). B) Similar to the method of Example 11B), 108.38 g (0,506 mol) of epoxide was reacted with 232.32 g (2 mol) of hydroxybutyl vinyl ether and 6.81 g of dibutyl thorium oxide until GC again detected the starting reactant (11 hours). After removing excess butyl vinyl ether, the residue was extracted with water to obtain 150.12 g (98.22¾ theoretical yield) of the desired product. Example 16 Mix the ingredients at 6 0¾ and stir under K until a clear solution appears: 48.4 g of 3,4-epoxycyclohexylmethyl-3 ^ * 4'-epoxycyclohexane carboxylate (Ara 1 dit®CY179 -5 2-This paper scale is applicable to the Chinese National Standard (CNS) A4 format (210X297mm). Threading (please read the precautions on the back before filling out this page). Five Invention Instructions (h ) G 8

6 〇2 YD A7 B7 ® t • 1 da Γ A / l \ ether propylene glycol diol di® re E ο t Γ as / IV allyl pentaerythritol hydrochloride four grams of quaternary gram of gram 2 6 3 9 9 3 e Γ UC a V ο Ν / fv dioctyl hydrochloride diammonium dihydrochloride A m double grams 6 ο ο 7 3 Θ grams 8 〇 Ketophenyl hexane ring Base hydroxyl e Γ UC a ε Γ (please read the note Ϋ on the back before filling in this page) -installed-4 8 1 * a Γy c gram 8ο 6 s

4 7 9 6 IVU helium 5 in ·, ο) XV 8 ο 3 3. (Ο s X • 7 a. Ρ 5 Γη4 1 is 2 inches and 1 foot is a degree of continuous bonding, and the following compound is mixed with cadmium } Qualitative 2 m m cM \ with J engraved m)) Type 8 is the modulus that the embryo can shoot. The model meter is made by the object * The shot according to the order of the line is 7 S 2 I 5 is manufactured according to dy R ο R according to 1., L oa (sp instrument IM test 4 4 5 is the number of EM / IV modulo I bombs% test 3 ο. Ο 3 5 2 ® is the d rate y long ο Stretch 1 split L to tear 7 of M to get 2 to measure 5 to R) Ran Zhong minutes: ο Quality 3 Sex shot under the M line to determine the purple and then type. The embryo of the clock bell is meristematic ο, 3 after the heat is added. C hard ο all 3 finished 1 The paper standard in the future applies to the Chinese National Standard (CMS) Α4 specification (210Χ297 mm) 322469 A7 B7 2 5 8 6 Μ P a; 2% 7 k J / cm V. Description of the invention (elastic Modulus: Elongation after tearing: Impact strength 8 (according to IS0179 / 1D) Curl factor: a 0.12 (Μ "textile" structure form made samples for testing * reference "Rapid Prototyping and Manufacturing, Fundamentals of Stereolithography, PF Jacobs ed., SME 1 9 9 2, page 2 5 6). Example 1 7 Mix and mix the following ingredients at 6 until a clear solution appears: 48 · 4 g of 3,4-epoxycyclohexylmethyl-3 ' , 4, —Epoxycyclohexane carboxylate (Ara 1 dit®CY179 18 g vinyl ether compound of Example 3; 20 g trifunctional hydroxyl-terminated polycaprolactone; 6 g dipentaerythritol Pentaacrylate (S art ome r ® 3 9 9); 6 grams of bisphenol A diglycidyl dienoate (Nova cure @ 3 7 0 0); 0 · 8 grams of 1 monohydroxycyclohexylbenzene Ketone (I rgacure © 18 4); -54- This paper scale is applicable to the Chinese national standard falcon (CNS) A4 specification (210X297 public daughter) II Ml IIIIIII Order IIIII (please read the precautions on the back before filling in this page) A7 B7 (A) 4 5. Description of the invention 0 · 8 g Cyracure®UVI6974 ° The viscosity of the mixture is 387mPa · s (30 ° C), Under the helium / cadmium laser, a molded object with a size of 45 · 7x0 · 38x0 · 5 1 mm (irradiation energy of 80mJ / cm1 2 3) was produced. After irradiation, the molded object (so-called green embryo model) immediately had Properties under K: modulus of elasticity (E-modulus) = 90. 8MPa; tear elongation is 70%. After complete hardening, the green embryo model is irradiated with ultraviolet rays for 30 minutes and then heated at 1 3 0 ° C for 3 0 Min. Then determine the properties under K: Elastic transverse number: 2663MPa; Elongation after tearing ·· 16 · 8% Impact strength 42kJ / cm2 (according to IS0179 / 1D) Curling factor: 0 · 013 ("textile" structure morphology molding ) Example 1 8 Mix at 60 ° C and stir the ingredients under M until a clear solution appears: 48.4 g of 3,4-epoxycyclohexylmethyl-3'epoxycyclohexanate after-salt ( Ara 1 dit® CY179 binding (please read the precautions on the back before filling this page) 1 8 grams of vinyl in Example 4 Ether compound; 2 20 grams of trifunctional hydroxyl-terminated polycaprolactone 3 -55- 322469 V. Description of the invention (#) A7 B7 6 grams of dipentaerythritol pentapropionate;!: Xilate (S art ome r ® 3 9 9); 6 g of bisphenol A diglycidyl diacrylate (No vacure ® 3 7 0 0); 0 · 8 g of 1 monocyclohexylbenzylamine (Irgacure © 18 4); 0.8 grams of Cyracure® UVI6974. The viscosity of the mixture is 281mPa · s (30¾), under the ^ / cadmium laser • made of 45. 7x0 · 38x0 · 51 1 mm molded object (irradiation energy is 160mJ / cm2), after irradiation, the molded object (The so-called green embryo model) immediately has the following properties: elastic modulus (E modulus) = 244MPa; tear elongation is 86%. After being completely hardened, the green embryo model was irradiated with ultraviolet rays for 60 minutes, and then heated at 1 3 0¾ for 30 minutes. Then determine the properties under K: Elastic modulus: Elongation after tearing: Impact strength (according to IS0179 / 1D) Curling factor: ("textile" structure morphology molded product) 3 0 8 3 Μ P a; 8-1 96 31 · 91 ^ υ / ί; ιτι2 0-0017-order (please read the precautions on the back before filling in this page) Example 1 9 5 6 The paper size is applicable to China National Standard (CNS) Α4 specification (210Χ297mm) V. Invention Description (β) A7 B7 at 60 t: Mix and stir the ingredients under M until a clear solution appears · 48 · 4 g of 3,4-epoxycyclohexylmethyl-3 ', 4 epoxycyclohexyl Alkyl carboxylate (Ara 1 dit®CY179 1 8 g 2 0 g 6 g 3 9 9); 6 g @ 3 7 0 0 〇 · 8 ® 1 8 4) Ο · 8 mixture / cadmium laser millimeter Molding 8/7 5 100% modulus of elasticity after complete hardening: Tensile strength (elongation impact strength after tearing of the vinyl ether compound of Example 10; trifunctional hydroxyl-terminated polycaprolactone; dipentaerythritol penta Acrylic acid salt (Sa rt ome r® bisphenol A diglycidyl dienoate (No vacur); gram of 1 monohydroxycyclohexyl phenyl ketone ( I rt The viscosity of Cyracure® UVI69 is 224mPa's (under 3 Ο, the size is 40 · 0x4 · 2 (textile type), after irradiation, the modulus of the molded object measured according to the bending test is 4 3 , The embryo model was heated at 6 ° C for 30 minutes by UV irradiation. Then, the lower M 2 7 1 8 Μ gac 7 4 ° t), 5x2 I SO 6 Μ P 0 minute mass: Pa; in helium • 5 17 a 0. Binding line (please read the precautions on the back before filling in this page) I SO rate: R 5 2 7) 6 3 Μ P a 7 · 3% 2 2 · 5 k J / 57 Standard (CNS) A4 specification (210X297 gong) A7 ^ 22469 B7 5. Description of the invention (ft) (according to DIN 52.4 53) Example 2〇48 · 4 grams of 3,4 monoepoxycyclohexylmethyl-3 ' , 4 '-epoxycyclohexane carboxylate (Ara 1 dit® CY179); 7 g of the vinyl ether compound of Example 15; 20 g of epoxypropylated mycel oil (He 1 oxy®5〇5 ; 18 grams of Polyvinyl Polyol (Desmophen®85〇) 95 grams of dipentaerythritol pentaacrylate (S art ome r © 3 9 9); Ο. 8 grams of Irgacure® 184; 0.8 grams of triaryl Gundam Fluoroantimonate inhibitor (Cyra cur ® UVI 6 9 7 4) ° The viscosity of the mixture is 6 0 0 m P a · s (3 0 cC) 〇 The elastic modulus (E modulus) after the laser hardening substance is After 2 0 1 呓 Μ P a ° was completely hardened, the green embryo model was irradiated with ultraviolet rays for 60 minutes and then heated at 100 ° C for 30 minutes. Then determine the following properties: Modulus of elasticity: 2043MPa Tensile strength 47.7MPa Elongation after tearing: 16% -58- This paper scale is applicable to China National Standard (CNS) Α4 specification (210X297mm) I Threading (please read first Note on the back and then fill out this page) δ A7 322469 B7 V. Description of the invention (0) Impact strength 37kJ / cm2 Curling factor: 0% ("textile" structure morphology molded product) Example 2 1 Μ under the composition of 6 0C- Mix and stir: 48 · 4 g of 3,4-epoxycyclohexylmethyl-3 ', 4 / —epoxycyclohexane carboxylate (Aradit® CY179); 1 2 g Example 1 5 Vinyl ether compound; 20 g glycidyl carbendazim oil (He 1 oxy®505; 13 g polycoolol (De smo phen®850) t 5 g trifunctional, hydroxyl-terminated polycaprolactone Acetamide (Tone® 0 3 0 1); 1.6 grams of triaryl cynofluoride antimonate inhibitor (Cyracur ® UVI 6 9 7 4) ° The viscosity of the mixture is 400 mPa · s (3 0 ° C). Lei The modulus of elasticity (E-modulus) after shot hardening is 348 · 4 Μ P a ° After complete hardening, the green embryo model is irradiated with ultraviolet rays for 60 minutes Then heat at 100 ° C for 30 minutes. Then determine the following properties: Elastic number: 719MPa -59- This paper scale is applicable to China National Standard Falcon (CNS) Α4 specification (210Χ297mm) Binding line I (please read the back first Please pay attention to this item and fill in this tile) I ~ ~ 57

A ^) / _ \ Description clearly sent 'Five

7 B 7) 2 objects 5 make R modal ο shape S configuration I rate knot {length: ”degree of elongation after weaving strength due to spinning cracks” tear resistance f 8 2 5 5% 4 a P Μ% 8 7 2 2 Exemplification: the base mixes the base and mixes the cyclohexyl mixed base to oxidize the I ring P-ο 4 6, under 3 parts of the gram 8 M4 3 4 9 7 1X YC @ t ·, ί 物 d 合 1 A ether r group A ene 丨 the acid of the ethyl salt 3 carboxyl group alkyl hexane hexyl ring 8 group 1 oxo ring e Γ UC a V ο N / IV ester acid allyl diyl propoxy ring A) cool) double ο G ο 6 7 3 ® re E otras -fv ester acid allyl pentaerythritol tetrapentaerythr 2 g 6 9 9 3 ® eη ο τ — \ 0 acetylene polyhexyl terminal hydroxy group bb food official three g} 1 2 ο 3ο ----------- Install-(please read the precautions on the back before filling in this page) Threading 1 · 6 g diphenyl hexafluoroarsenate; 0 * 8 g I rgacure ®184 ° The viscosity of the mixture is 450 mPa, s (30 ° C). Under the ammonia / cadmium laser, a molded article with a size of 40x4 · 3x3.8 mm was produced. After irradiation, the E-modulus of the molded article measured according to I SO 1 78/75 bending test was 1 4 4 · 9 Μ Pa. After being completely hardened, the green embryo model is irradiated with ultraviolet rays for 60 minutes, then -60- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 322469 Elastic modulus: tensile strength Elongation after tearing: A7 B7 5. Description of the invention (θ) Heat at 100C for 30 minutes. Then determine the following properties: 2 8 1 1 Μ P a 6 2 · 1 Μ P a 7 · 5% · -6 1- This paper music scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) n Pack n order Line (please read the notes on the back before filling this page)

Claims (1)

Announcement A8 B8 C8 D8 Amendment Year ^ / 1 afeli · 28 supplement, patent application scope 1 · A vinyl ether compound, which can flow at room temperature, it has the following formula H2C = CH-0 A, where The symbols of the following formulas are defined as follows: A is a z-valent group selected from the following formulas (1), .. (2), (3) and (4) (2)-(cxh2x) -〇 \ ch2I CH R2〇 / \ (： Η2-0- (3) —— (CSH2) —oc— [D]-R] — (CsH2s > R14 z-1 CH 2-z; ^ policy;, order (please read the precautions on the back before filling this page) Ministry of Economic Affairs Printed by the Central Bureau of Rigidity and Consumer Cooperatives oII (4) (CsH2s) -〇-C- (CtH2t)--(CsH2s) -〇-C- (CtH2t> O [D] is the following formula 1-This paper The standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) [E] \ R 2-1 15 322469 ABCD patent application scope ο Γ ο / \ / \ (5) — (CxH2x) —CH-CH-( CuH2u) —CH—CH—v (CyH2) —; [E] is (:! One or C2 alkylene; R 1 is selected from alkylene containing 2 to 4 carbon atoms, phenyl and the following formula base Wherein R and R3 are independently hydrogen atoms or methyl groups; R 2 is selected from the group consisting of Ο / \-ch2-ch—ch2 O II ο 11 4 j —C — NH — R — NH — C — OR; R 5 is (please read the precautions on the back and then fill out this page) clothing. Printed by the Ministry of Economic Affairs Central Standards Bureau Negative Work Consumer Cooperative. 〇O CH3 II III-(C2H4) -0-C-CH = CH2,. ( C2H4) -0-CC = ch2 -ch2-ch = ch2 shows d Rs is the formula R8 — [G 3 — 2z price base of R9, of which -2- this paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X: 297 mm) 3 22469 A8 B8 C8 D8 Patent scope R3 — Starting from the carbon atom Λα #-(cxh2x) -o, r2o (fH I, CPH (6) of formula (6) in formula (2) to form a cycloalkyl group containing 6 ring carbon atoms; R9-starting with another The carbon atom Λα of the group of formula (6) / forms a cycloalkyl group containing 6 ring carbon atoms; i G] is a structural unit selected from the following formula: 〇0 0 II 'I' 丨 丨 -C * 〇_CH2- * CH2_0 · C * (C | 1H2) 1) 'C * 〇'CH2_ (Please read the precautions on the back before filling in this page) Clothing. .IT Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs h is 2 to 4. Integers; R1 4 and R1 s are each hydrogen atoms, or when [E] is C, each is a hydrogen atom or together form a methylene group; s is an integer from 2 to 4; t is an integer from ◦ to 2; u is An integer of 1; v is an integer of 0 or 1; X and y are integers of 2 to 8; and z is an integer of 1 or 2. 2 A compound as claimed in item 1 of the patent application, which has the following formula -3 -The standard of Kanlou local paper music applies to China National Standard (CNS) A4 regulation (210X297mm) 964 ABCD patent application scope or Rio 0-0 II II -CH2-0-C- (CH2) hC-0-CH2- (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs R1 ° and R1 3 One of the two is the formula H2 C = CH — 0 — (C Η 2) χ — Ο —, the other is the formula R2 Ο —, the same, R 1 1 and! ^ 1 2 One of the two is Hz C = CH — Ο — (C H2) x-0 —, and the other is the formula R2 〇—, where x and h are independently integers from 2 to 4. 3. A compound as claimed in item 1 of the patent application, wherein A is a group of formula (4), R1 4 and R1 5 are both hydrogen atoms and z is 1. 4 * If the compound of the first item of the patent application scope, it has the following formula. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 322469 ABCD 々, patent application scope — (CH2) -0-CH = CH2. II ο Printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5 ·-A liquid composition formulated for the three-dimensional lithography method, the composition including: 5 to 60% by weight The vinyl ether compound as claimed in item 1 of the patent application; 〇 to 4 b% by weight of mono-, di- or polyfunctional acrylate or methacrylate; 3 ◦ to 80% by weight of di- or multi-functional group Epoxy compound; 0 to 5% by weight of free radical photoinitiator; 0.5 to 5% by weight of cationic photoinitiator; 0 to 40% by weight of hydroxyl-terminated polyether or polyester; and 0 One or more additives up to 10% by weight. 6. A method for preparing a three-dimensional space object from a composition as claimed in item 5 of the M patent stereolithography, which includes the steps in which the entire surface of the composition layer surface or the predetermined pattern is exposed to ultraviolet rays / Visible light source irradiation, so that the layer of the desired thickness is cured in the irradiated area, and then a new layer of composition is formed on the cured layer, the new layer on all surfaces or in the preset picture-^^ 1 νϋ «^^^^ 1 mw nn 1- m ^ i — ^ ϋ — ^ nw * ('3 * m (please read the precautions on the back and then fill in this page) This paper size is applicable to China National Standard (CNS) Α4 specification (210Χ297mm ) 322469 1 VI. The scope of the patent application can be derived from each other. The part and the object's shot-to-air illuminance and the three-layered new structure plus the overburden layer are re-enhanced and solidified. (Please read the precautions on the back before filling out this page) The paper standard printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210X297 mm)